Size evolution study of “molecular” and “atom-in-cluster” polarizabilities of medium-size gold clusters

Abstract

A study on static polarizabilities for a family of gold clusters (Au(n), n = 6, 12, 20, 34, 54) is presented. For each cluster, a density functional theory perturbation theory calculation was performed to compute the cluster polarizability and the polarizability of each atom in the cluster using Bader's "quantum theory of atoms in molecules" formalism. The cluster polarizability tensor, α(cluster), is expressed as a sum of the atom-in-molecule tensors, α(cluster)=∑(Ω)α(Ω). A strong quadratic correlation (R(2) = 0.98) in the isotropic polarizability of atoms in the cluster and their distance to the cluster center of mass was observed. The cluster polarizabilities are in agreement with previous calculations.

Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

“…Figure shows the gold cluster complex Au 4 −S−C 6 H 4 −S′−Au′ 4 , which is composed of a benzene ring linking two gold nanoclusters Au 4 through sulfur atoms . The nature of the sulfur–gold and gold–gold chemical bonds in these types of complexes was previously analyzed in detail by us using ZORA‐QTAIM . Thus, we focus here only on the new features on the QTAIM topology (chemical bonding) in these gold complex systems due to relativistic effects.…”

“…Both singlet and triplet spin multiplicities were considered. QTAIM topology and properties were determined by an unrestricted single‐point (SP) calculation at the optimized geometry using the QTAIM module in ADF …”

“…QTAIM topology and properties were determined by an unrestricted single-point (SP) calculation at the optimized geometry using the QTAIM module in ADF. [56][57][58][59][60]…”

“…The nature of the sulfurgold and gold-gold chemical bonds in theset ypes of complexes was previously analyzed in detail by us using ZORA-QTAIM. [43,[54][55][56][57][58][59][60] Thus, we focus here only on the new features on the QTAIM topology (chemical bonding) in these gold complex systemsdue to relativistic effects.…”

Size evolution relativistic DFT-QTAIM study on the gold cluster complexes Au4-S-CnH2n-S′-Au4′ (n = 2–5)

“…For the two lowest energy isomers of each complex size, n=2-5, (see Figure 1), an all-electron self consistent field (SCF) single point (SP) ZORA DFT calculation followed by a QTAIM calculation was performed at the optimized geometry. The relativistic ZORA-QTAIM calculations were performed using our ultrafast method as implemented in ADF [40][41][42]. For both geometry optimization and SP calculations, the (generalized-gradient-approximation) Perdew-Burke-Ernzerhof (PBE) [43] functional and a triplepolarized Slater (TZP) basis set were used.…”