A DFT study on equilibrium geometries, stabilities, and electronic properties of small bimetallic Na-doped Au_n (n = 1-9) clusters: comparison with pure gold clusters

摘要

A systematic study on the geometric structures, relative stabilities, and electronic properties of small bimetallic Au _n Na (n = 1-9) clusters has been performed by means of first-principle density functional theory calculations at the PW91PW91 level. The results show that the optimized ground-state isomers adopt planar structures up to n = 5, and the Na-capped geometries are dominant growth patterns for n = 6-9. Dramatic odd-even alternative behaviors are obtained in the second-order difference of energies, fragmentation energies, highest occupied-lowest unoccupied molecular orbital energy gaps, and chemical hardness for both Au _n Na and Au _n+1 clusters. It is found that Au₅Na and Au₆ have the most enhanced stability. Here, the size evolutions of the theoretical ionization potentials are in agreement with available experimental data, suggesting a good prediction of the lowest energy structures in the present study. In addition, the charge transfer has been analyzed on the basis of natural population analysis.