Structures and Electronic Properties of TMPb16−/0/+ (TM = Sc, Y, Ti, Zr, Hf) Clusters

Abstract

In this work, the structures and electronic properties of anionic, neutral, and cationic TMPb₁₆^−/0/+ (TM = Sc, Y, Ti, Zr, Hf) clusters were studied through a genetic algorithm (GA) code with density functional theory (DFT) calculations. The results show that anionic TMPb₁₆⁻ (TM = Sc, Y, Ti, Zr) and neutral TMPb₁₆ (TM = Ti, Zr, Hf) clusters adopt the Frank–Kasper (FK) polyhedron as the geometric structure, while TMPb₁₆ (TM = Sc, Y, Hf⁻) and all cationic states of these clusters prefer a fullerene-like bitruncated square trapezohedron. In these clusters, the gain and loss of electrons in transition metals (TM) are similar and very small, with only Hf atom as the electron donor. The average binding energy of cationic TMPb₁₆ is 0.02 and 0.1 eV higher than that of its anionic and neutral states, respectively. All these TMPb₁₆ (TM = Sc⁻, Y⁻, Ti, Zr, Hf) clusters with 68 electrons show superatomic features with the electronic shell configuration of (1S)²(1P)⁶(1D)¹⁰(1F)¹⁴(2S)²(1G)¹⁸(2P)⁶(2D)¹⁰ as same as that of TMSn₁₆ (TM = Sc⁻, Y⁻, Ti, Zr, Hf) clusters.