Dataset Information

Size Effect on Aurophilic Interaction in Gold-Chloride Cluster Anions of Au _n Cl _n+1 ^- (2 ? n ? 7).

ABSTRACT: Aurophilic interaction plays a very important role in gold-related clusters. Here, we investigate the Au _n Cl _n+1 ^- (n = 1-7) cluster ions using Fourier transform ion cyclotron resonance mass spectrometry in combination with theoretical calculations. Three cluster ions of Au₂Cl₃ ^-, Au₃Cl₄ ^-, and Au₄Cl₅ ^- show their remarkable intensities in the mass spectrum. Geometric structure optimizations for Au _n Cl _n+1 ^- (n = 1-7) were performed on the MP2 level. The results show that the most stable structures of Au _n Cl _n+1 ^- (n = 2-7) are all characterized by a zigzag structure. Furthermore, it can be found that the aurophilic interactions containing terminal gold atoms strengthen with the increase of total gold atoms and progressively stabilize for large clusters of Au₆Cl₇ ^- and Au₇Cl₈ ^-, whereas the aurophilic interactions between nonterminal adjacent gold atoms stabilize at n = 5.

SUBMITTER: Ma Y

PROVIDER: S-EPMC6649055 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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Size Effect on Aurophilic Interaction in Gold-Chloride Cluster Anions of Au n Cl n+1 - (2 ≤ n ≤ 7).

Ma Yuan Y Bian Shen S Shi Yingying Y Fan Xingting X Kong Xianglei X

ACS omega 20190109 1

Aurophilic interaction plays a very important role in gold-related clusters. Here, we investigate the Au n Cl n+1 - (n = 1-7) cluster ions using Fourier transform ion cyclotron resonance mass spectrometry in combination with theoretical calculations. Three cluster ions of Au2Cl3 -, Au3Cl4 -, and Au4Cl5 - show their remarkable intensities in the ...[more]

PMID: 31459354

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Project description:In this contribution, we propose a deeper understanding of the electronic effects affecting the nucleation of water around the Au+ and Hg2+ metal cations using quantum chemistry. To do so, and in order to go beyond usual energetical studies, we make extensive use of state of the art quantum interpretative techniques combining ELF/NCI/QTAIM/EDA computations to capture all ranges of interactions stabilizing the well characterized microhydrated structures. The Electron Localization Function (ELF) topological analysis reveals the peculiar role of the Au+ outer-shell core electrons (subvalence) that appear already spatially preorganized once the addition of the first water molecule occurs. Thus, despite the addition of other water molecules, the electronic structure of Au(H2O)+ appears frozen due to relativistic effects leading to a maximal acceptation of only two waters in gold's first hydration shell. As the values of the QTAIM (Quantum Theory of Atoms in Molecules) cations's charge is discussed, the Non Covalent Interactions (NCI) analysis showed that Au+ appears still able to interact through longer range van der Waals interaction with the third or fourth hydration shell water molecules. As these types of interaction are not characteristic of either a hard or soft metal cation, we introduced the concept of a "pseudo-soft" cation to define Au+ behavior. Then, extending the study, we performed the same computations replacing Au+ with Hg2+, an isoelectronic cation. If Hg2+ behaves like Au+ for small water clusters, a topological, geometrical, and energetical transition appears when the number of water molecules increases. Regarding the HSAB theory, this transition is characteristic of a shift of Hg2+ from a pseudosoft form to a soft ion and appears to be due to a competition between the relativistic and correlation effects. Indeed, if relativistic effects are predominant, then mercury will behave like gold and have a similar subvalence/geometry; otherwise when correlation effects are predominant, Hg2+ behaves like a soft cation.

Dataset Information

Size Effect on Aurophilic Interaction in Gold-Chloride Cluster Anions of Au _n Cl _n+1 ^- (2 ? n ? 7).

Publications

Size Effect on Aurophilic Interaction in Gold-Chloride Cluster Anions of Au <sub><i>n</i></sub> Cl <sub><i>n</i>+1</sub> <sup>-</sup> (2 ≤ <i>n</i> ≤ 7).

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OmicsDI is part of the ELIXIR infrastructure

Dataset Information

Size Effect on Aurophilic Interaction in Gold-Chloride Cluster Anions of Au n Cl n+1 - (2 ? n ? 7).

Publications

Size Effect on Aurophilic Interaction in Gold-Chloride Cluster Anions of Au <sub><i>n</i></sub> Cl <sub><i>n</i>+1</sub> <sup>-</sup> (2 ≤ <i>n</i> ≤ 7).

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Size Effect on Aurophilic Interaction in Gold-Chloride Cluster Anions of Au _n Cl _n+1 ^- (2 ? n ? 7).