Theoretical prediction for the structures of gas phase lithium oxide clusters: (Li₂O)_n (n = 1–8)

Abstract

We apply genetic algorithm combining directly with density functional method to search the potential energy surface of lithium-oxide clusters (Li 2 O) n up to n ¼ 8. In (Li 2 O) n (n ¼ 1-8) clusters, the planar structures are found to be global minimum up to n ¼ 2, and the global minimum structures are all threedimensional at n ! 3. At n ! 4, the tetrahedral unit (TU) is found in most of the stable structures. In the TU, the central Li is bonded with four O atoms in sp 3 interactions, which leads to unusual charge transformation, and the probability of the central Li participating in the bonding is higher by adaptive natural density partitioning analysis, so the central Li is in particularly low positive charge. At large cluster size, distortion of structures is viewed, which breaks the symmetry and may make energy higher. The global minimum structures of (Li 2 O) 2 , (Li 2 O) 6 , and (Li 2 O) 7 clusters are the most stable magic numbers, where the first one is planar and the later both have stable structural units of tetrahedral and C 4v .

Global optimization of clusters using electronic structure methods

“…Genetic algorithm Main-group elements and coinage metals Li, [117] Cs, [119] B, [118] Al, [138] Ga, [139] Si, [140] Sn, [130,[134][135][136] Pb, [141] P, [142] As, [142] Bi, [143] Cu, [126,144] Ag, [94,125,126] Au [94,125,126,145] Nanoalloys Na-Si, [127] Sn-Bi, [146,147] Ag-Cu, [126] Au-Cu, [126] Au-Ag [94,125] Oxide a and other systems Li-O, [148] Be-O, [149] Mg-O, [150,151] B-O, [152] Al-O, [153] Ce-O, [154] W-O, [155] Li-F, [156] Al-H, [157] B-C, [158] Li-Al-B, [159] H 2 O-H [160] Complex systems Ag-Lig, [161] Au-Surf, [131,162] Au-Pd-Surf [162] Basin hopping Homoatomic B, <...>…”

Structural evolution of (Au2S)n (n = 1–8) clusters from first principles global optimization

“…[34][35][36][37] GA is a search heuristic that mimics the process of natural selection. [34][35][36][37] GA is a search heuristic that mimics the process of natural selection.…”

Theoretical investigation of geometry and stability of small lithium-iodide LinI (n= 2-6) clusters

“…A subset of the clusters of interest is small alkali metal clusters, particularly lithium clusters, which are computationally accessible yet physically and chemically complex. Lithium ability to form clusters with various elements is well known; in particular, the structural and bonding properties of boron‐lithium clusters, aluminum doped lithium clusters, mixed silicon‐lithium clusters, Li n Ge, Li n O, and (Li 2 O) n clusters were investigated; furthermore, the properties of small lithium halide, Li n F n −1 clusters, mixed sodium‐lithium, hydrogenated lithium clusters, or small bimetallic Li n Cu m clusters were also examined; the interaction with carbon monoxide or with various functional groups was recently reported. The primary interest in studying heterogeneous lithium clusters was the characterization of changes in bonding, and consequently their properties, from small clusters to the limit of delocalized electrons in the bulk metal (where heteroatoms are treated as impurity).…”