Relativistic density-functional studies of naked and ligated gold clusters

Abstract

Electronic structure investigations on a broad range of gold compounds, including naked and ligated gold clusters, are reviewed. The calculations have been carried out with a recently introduced relativistic variant of the linear combination of Gaussian-type orbitals density-functional (LCGTO-DF) method which affords all-electron investigations for very large systems. The accuracy of the method will be evaluated for the gold dirner. Then the electronic structure of the naked cluster AuSS is studied, both in Ih and Oh symmetry. Nonrelativistic and relativistic results obtained by the present method are compared to those of the much simpler jellium model. Since triphenylphosphine is among the most common ligands in gold chemistry a series of mononuclear gold phosphine compounds MeAuPR, with increasingly complex ligands PR3 ( R = H, CH3, CSH6) is discussed. The calculations reveal the success and the limitations of simpler phosphines often employed as model ligands in theoretical studies. Some aspects of the phosphine gold interaction in these simpler compounds cany over to the main group element centered gold clusters.Thereby one arrives at a rationalization ofthe particularly high stability of the carbon-centered octahedral cluster cation [ ( R3PAu)&] '+ as compared to the neighboring isoelectronic boron and nitrogen-centered clusters.

The application of effective core potentials in heavy atom molecules: A study of small gold clusters and molecules as a function of theoretical method

“…ECP ‫ס‬ effective core potential; DFT ‫ס‬ density functional theory. tion calculations at both the singles ‫ם‬ doubles level [28] and also with triplet energy corrections [8], the LCGTO-DF method described earlier [8] and a coupled electron pair approximation (CEPA) calculation using a pseudopotential [33]. With the exception of the LCGTO-DF results, all of these cited calculations underestimate the IP.…”

“…Our results provide good agreement in comparison to the experimental properties. The only previous study has been that of Rö sch et al [8] and Hä berlen and Rö sch [9], using the LGGTO-DF method and a large basis set. The authors report a Au-C bondlength of 2.00Å and a Au-P bondlength of 2.29Å , nearly identical to the experimental values.…”

“…For example, Lamare and Michel-Calendini [7] have explored the structure of the Au 13 cluster using the local density approximation (LDA) framework. Rö sch and co-workers [8] have developed a quasirelativistic variant of the linear combination of Gaussian-type orbitals density functional (LCGTO-DF) method and applied it extensively to naked and ligated gold clusters as well as to ligated single Au atoms [9]. The method employs large basis sets and has been shown to be very effective in reproducing available experimental data.…”

Band Structure, Morphology, Functionality, and Size- Dependent Properties of Metal Nanoparticles

“…The small clusters with fewer than 20 atoms were thoroughly investigated by several research groups [29,30]. Some of the earliest work on large systems focused on symmetrical structures.…”

“…Some of the earliest work on large systems focused on symmetrical structures. Haberlen et al [29] examined octahedral and icosahedral Au 55 using the Vosko, Wilks and Nusair (VWN) functional and found that the Kohn-Sham orbitals and their energy orderings agreed well with a jellium model once energy level splittings due to symmetry reduction were considered.…”