| dc.description |
The present work discusses the capability of 20-nanogold low-energy clusters to encage atomic and molecular species and investigates hollow cages of Au<sub>20</sub>, their structures and stability, and their void reactivity. We begin with performing a systematic computational search of hollow cages on the potential energy surface of doubly anionic Au<sub>20</sub> which, according to the experimental abundance spectra of Au<sub>20</sub><sup>2−</sup>, has an approximately degenerate ground state. Since the computed second electron affinity of the neutral tetrahedral ground-state cluster Au<sub>20</sub>(T<sub>d</sub>) agrees well with the experimental value EA<sub>2</sub><sup>expt</sup>(Au<sub>20</sub>), this ground state is thus partly occupied by [Au<sub>20</sub>(T<sub>d</sub>)]<sup>2−</sup> whose original neutral T<sub>d−</sub>symmetry is broken. Determining the other, yet unknown isomer and applying 'reverse' charge state mappings Z −2 ⇒ Z 0, ±1, we identify stable and low-energy Au<sub>20</sub> hollow cages which are further studied from different angles and compared with Au<sub>20</sub><sup>Z</sup>(T<sub>d</sub>). The void reactivity of these 20-nanogold hollow cages is the key theme - it is suggested that, together with the global characteristics, such as the ionization potential and electron affinity, the molecular electrostatic potential and HOMO-LUMO patterns are actually tools that may shed a light on the general features of voids of these golden fullerenes and their capability to encage H and Li. The confinement character of the studied golden fullerenes is compared with the classical examples, C<sub>60</sub> in particular. |
