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Effect of Charge and Phosphine Ligands on the Electronic Structure of the Au₈ Cluster.

ABSTRACT: In this work, we use density functional theory calculations with a hybrid exchange-correlation functional and effective core pseudopotentials to determine the geometry of bare and phosphine-protected Au₈ nanoclusters and characterize their electronic structure. Au₈ clusters were bonded to four and eight PH₃ ligands in order to evaluate the effect of ligand concentration on the electronic structure, while different positional configurations were also tried for four ligands attached to the cluster. We show that the neutral clusters become more nucleophilic as the ligands bind to the clusters at stable sites. The ground-state planar configuration of Au₈ is maintained depending on the concentration and position of ligands. The effect of ionizing to the +2 charge state results in disruption of planar geometry in some cases because of inoccupation of a molecular orbital with the Au-Au bonding character. Natural bond order charge analyses showed that Au atoms oxidize upon ionization, instead of phosphine. The net positive charge makes the clusters more electrophilic with a capacity to absorb electrons from nucleophiles depending on the concentration and position of ligands and on the concentration of low-coordinated gold atoms. Besides, ionization energies and electron affinities were calculated through different mechanisms, finding that both variables are much higher for charged systems and change inversely with the concentration of ligands.

SUBMITTER: Burgos JC

PROVIDER: S-EPMC6648428 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

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Effect of Charge and Phosphine Ligands on the Electronic Structure of the Au8 Cluster.

Burgos Juan C JC Mejía Sol M SM Metha Gregory F GF

ACS omega 20190524 5

In this work, we use density functional theory calculations with a hybrid exchange-correlation functional and effective core pseudopotentials to determine the geometry of bare and phosphine-protected Au8 nanoclusters and characterize their electronic structure. Au8 clusters were bonded to four and eight PH3 ligands in order to evaluate the effect of ligand concentration on the electronic structure, while different positional configurations were also tried for fou ...[more]

PMID: 31460005

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Project description:In order to increase the understanding of the recently synthesized Au70S20(PPh3)12 cluster, we used the divide and protect concept and superatom network model (SAN) to study the electronic and geometric of the cluster. According to the experimental coordinates of the cluster, the study of Au70S20(PPh3)12 cluster was carried out using density functional theory calculations. Based on the superatom complex (SAC) model, the number of the valence electrons of the cluster is 30. It is not the number of valence electrons satisfied for a magic cluster. According to the concept of divide and protect, Au70S20(PPh3)12 cluster can be viewed as Au-core protected by various staple motifs. On the basis of SAN model, the Au-core is composed of a union of 2e-superatoms, and 2e-superatoms can be Au3, Au4, Au5, or Au6. Au70S20(PPh3)12 cluster should contain fifteen 2e-superatoms on the basis of SAN model. On analyzing the chemical bonding features of Au70S20(PPh3)12, we showed that the electronic structure of it has a network of fifteen 2e-superatoms, abbreviated as 15 × 2e SAN. On the basis of the divide and protect concept, Au70S20(PPh3)12 cluster can be viewed as Au4616+[Au12(µ3-S)108-]2[PPh3]12. The Au4616+ core is composed of one Au2212+ innermost core and ten surrounding 2e-Au4 superatoms. The Au2212+ innermost core can either be viewed as a network of five 2e-Au6 superatoms, or be considered as a 10e-superatomic molecule. This new segmentation method can properly explain the structure and stability of Au70S20(PPh3)12 cluster. A novel extended staple motif [Au12(µ3-S)10]8- was discovered, which is a half-cage with ten µ3-S units and six teeth. The six teeth staple motif enriches the family of staple motifs in ligand-protected Au clusters. Au70S20(PPh3)12 cluster derives its stability from SAN model and aurophilic interactions. Inspired by the half-cage motif, we design three core-in-cage clusters with cage staple motifs, Cu6@Au12(?3-S)8, Ag6@Au12(?3-S)8 and Au6@Au12(?3-S)8, which exhibit high thermostability and may be synthesized in future.

Dataset Information

Effect of Charge and Phosphine Ligands on the Electronic Structure of the Au₈ Cluster.

Publications

Effect of Charge and Phosphine Ligands on the Electronic Structure of the Au<sub>8</sub> Cluster.

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