Probing the structural evolution of ruthenium doped germanium clusters: Photoelectron spectroscopy and density functional theory calculations

Abstract

We present a combined experimental and theoretical study of ruthenium doped germanium clusters, RuGen− (n = 3–12), and their corresponding neutral species. Photoelectron spectra of RuGen− clusters are measured at 266 nm. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) are obtained. Unbiased CALYPSO structure searches confirm the low-lying structures of anionic and neutral ruthenium doped germanium clusters in the size range of 3 ≤ n ≤ 12. Subsequent geometry optimizations using density functional theory (DFT) at PW91/LANL2DZ level are carried out to determine the relative stability and electronic properties of ruthenium doped germanium clusters. It is found that most of the anionic and neutral clusters have very similar global features. Although the global minimum structures of the anionic and neutral clusters are different, their respective geometries are observed as the low-lying isomers in either case. In addition, for n > 8, the Ru atom in RuGen−/0 clusters is absorbed endohedrally in the Ge cage. The theoretically predicted vertical and adiabatic detachment energies are in good agreement with the experimental measurements. The excellent agreement between DFT calculations and experiment enables a comprehensive evaluation of the geometrical and electronic structures of ruthenium doped germanium clusters.

Probing the structural evolution and electronic properties of divalent metal Be2Mgn clusters from small to medium-size

“…Here we rely on the CALYPSO code [45][46][47] , which can quickly search the most stable structures of the clusters on the bases of the particle swarm optimization algorithm. The validity of this method for clusters structure predicting has been demonstrated by its successful application of various clusters [48][49][50][51][52][53][54][55] . In detail, trial structures of the clusters are ordered in generations in the process of searching.…”

Electronic structures of NbGen−/0/+ (n = 1–3) clusters from multiconfigurational CASPT2 and density matrix renormalization group‐CASPT2 calculations

“…Transition metal-doped germanium clusters are widely investigated because of their potential applications as building blocks for nanomaterials. [1][2][3][4][5][6][7][8] Because properties of clusters depend on their geometric structure and atomic composition, a large number of transition metal-doped germanium clusters have been studied to search for stable clusters. Experimentally, the mass-selected anion photoelectron spectroscopy was applied to probe the geometric and electronic structures of many transition metal-doped germanium clusters.…”

Probing on the Stable Structure of Silicon-Doped Charged Magnesium Nanomaterial Sensor: SiMgn±1 (N = 2−12) Clusters DFT Study

“…In recent years, there has been an increasing amount of reports on using atomic clusters together with the first-principle to predict new stable nanomaterials as potential sensors (Ding et al, 2015;Jin et al, 2015Jin et al, , 2016Xia et al, 2016;Li et al, 2017;Chen et al, 2018;Shao et al, 2019;Zhao et al, 2019;Zhang et al, 2020) such as nanomaterials of Zr-B, Ta-B and Fe-O systems, etc. Nanomaterials of silicon and magnesium are inevitable and are studied through their clusters structures.…”