Density functional study of structures, stabilities and electronic properties of AgAunλ(λ=0,±1;n=1-12){\rm{AgAu}}_n^\lambda \left( {\lambda = 0, \pm 1;n = 1 - 12} \right) clusters: comparison with pure gold clusters

Abstract

Abstract Geometrical structures, relative stabilities and electronic properties of neutral, cationic and anionic pure gold A u n + 1 λ {\rm{A}}u_{n + 1}^\lambda and Ag-doped bimetallic AgAu n λ ( λ = 0 , ± 1 ; n = 1 - 12 ) {\rm{AgAu}}_n^\lambda \left( {\lambda = 0, \pm 1;n = 1 - 12} \right) clusters have been systematically investigated by using density functional theory methodology. The optimized structures show that planar to three-dimensional structural transition occurs at n = 5 for cationic clusters. Due to strong relativistic effect of Au clusters, the ground state configurations of neutral and anionic bimetallic clusters favor planar geometry till n = 12. Silver atoms tend to occupy the most highly coordinated position and form the maximum number of bonds with Au atoms. The computed HOMO-LUMO energy gaps, fragmentation energies and second-order difference of energies show interesting odd-even oscillation behavior. The result indicates that AgAu5, AgAu 2 + {\rm{AgAu}}_2^ + and AgAu 2 - {\rm{AgAu}}_2^ - are the most stable clusters in this molecular system. The DFT based descriptors of bimetallic clusters are also discussed and compared with pure gold clusters. The high value of correlation coefficient between HOMO-LUMO energy gaps and DFT based descriptors supports our analysis. A good agreement between experimental and theoretical data has been obtained in this study.