First principles study on the structural evolution and properties of (MCl)<sub>n</sub> (n = 1–12, M = Cu, Ag) clusters

Tian, Zhimei; Cheng, Longjiu

doi:10.1039/c6ra01258b

Cited by 11 publications

(2 citation statements)

References 72 publications

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“…NICS-scan method is proposed by Stanger, which is similar to the screen method of aromatic center and has been used to predict the aromatic properties of molecules and clusters [52,53,54]. Here, we use NICS-scan method to further verify the existence of Au 4 superatoms and we have demonstrated the existence of Au 4 superatoms in Au 20 (SR) 16 , Au 28 (SR) 20 and Au 30 S 2 (SR) 18 clusters in our former work [19,36].…”

Section: Resultsmentioning

confidence: 99%

New Perspectives on the Electronic and Geometric Structure of Au70S20(PPh3)12 Cluster: Superatomic-Network Core Protected by Novel Au12(µ3-S)10 Staple Motifs

Tian

Cheng

2019

Nanomaterials

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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(μ3-S)8, Ag6@Au12(μ3-S)8 and Au6@Au12(μ3-S)8, which exhibit high thermostability and may be synthesized in future.

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Section: Resultsmentioning

confidence: 99%

New Perspectives on the Electronic and Geometric Structure of Au70S20(PPh3)12 Cluster: Superatomic-Network Core Protected by Novel Au12(µ3-S)10 Staple Motifs

Tian

Cheng

2019

Nanomaterials

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“…32,62 Herein, we use the non-covalent interaction (NCI) index approach to detect non-covalent interactions based on electron density and its derivatives, which has been successfully applied to investigate the weak interaction in a number of systems. [63][64][65] NCI index provides a rich representation of non-covalent interactions, such as, van der Waals interactions, hydrogen bonds, and steric repulsion. Besides the non-covalent interactions, NCI index can also provide representation for weak covalent interactions.…”

Section: Nci Analysismentioning

confidence: 99%

The nature of the multicenter bonding in π-[TCNE]₂²⁻ dimer: 4c/2e, 12c/2e, or 20c/2e?

Cui

Cheng

2017

RSC Adv.

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The dianion dimer of tetracyanoethylene (TCNE), p-[TCNE] 2 2À , represents an unusual class of organic compounds, that possess exceptionally long C-C bonding interactions ($2.96Å). It is twice that of conventional C-C bonds but shorter than the sum of the van der Waals radii. Experimental and computational studies best characterize the intradimer bonding as a multi-center C-C bond. A number of theoretical studies indicate that the p-[TCNE] 2 2À dimer exhibits long, four-centers/two-electron (4c/ 2e) C-C bonds. However, there is still some disputation about the number of centers involved in the multicenter bonding. This work focuses on quantitative understanding of the nature of the long, multicenter bonding in the p-[TCNE] 2 2À dimer. By the chemical bonding analysis, it is found that $68% of electrons in the long bond locate on the -CCgroups and the remaining locate on the -CN groups. The substituent effect is investigated by comparing the interaction energy curves of the [C 2 X 4 ] 2 2À dimer (X ¼ H, Cl and CN). The deep local well at 3.0Å for X ¼ CN indicates a strong bonding interaction. However, there is no obvious local well in the curves for X ¼ H and Cl, which indicates that the [C 2 Cl 4 ] 2 2À and [C 2 H 4 ] 2 2À dimer are unstable. Herein, the -CN plays an important role in the bonding of the p-[TCNE] 2 2À dimer, and it is more reasonable to take the long bond as 20c/2e (12 carbon plus 8 nitrogen). Moreover, we found an abnormal charge redistribution from TCNE to TCNE À , and the charge distribution of [TCNE] 2 2Àis very similar to that of TCNE À , which benefits the formation of the dianion dimer.

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Systematic study on the structures and properties of (Ag2S)n (n = 1–8) clusters

Song

Tian

2019

J Mol Model

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First principles study on the structural evolution and properties of (MCl)_n (n = 1–12, M = Cu, Ag) clusters

Abstract: Energetic gaps (E − Efit) and second differences of binding energies (Δ2E) for (CuCl)n and (AgCl)n clusters as a function of cluster size, n.

Cited by 11 publications

References 72 publications

New Perspectives on the Electronic and Geometric Structure of Au70S20(PPh3)12 Cluster: Superatomic-Network Core Protected by Novel Au12(µ3-S)10 Staple Motifs

New Perspectives on the Electronic and Geometric Structure of Au70S20(PPh3)12 Cluster: Superatomic-Network Core Protected by Novel Au12(µ3-S)10 Staple Motifs

The nature of the multicenter bonding in π-[TCNE]₂²⁻ dimer: 4c/2e, 12c/2e, or 20c/2e?

Systematic study on the structures and properties of (Ag2S)n (n = 1–8) clusters

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First principles study on the structural evolution and properties of (MCl)n (n = 1–12, M = Cu, Ag) clusters

Abstract: Energetic gaps (E − Efit) and second differences of binding energies (Δ2E) for (CuCl)n and (AgCl)n clusters as a function of cluster size, n.

Cited by 11 publications

References 72 publications

New Perspectives on the Electronic and Geometric Structure of Au70S20(PPh3)12 Cluster: Superatomic-Network Core Protected by Novel Au12(µ3-S)10 Staple Motifs

New Perspectives on the Electronic and Geometric Structure of Au70S20(PPh3)12 Cluster: Superatomic-Network Core Protected by Novel Au12(µ3-S)10 Staple Motifs

The nature of the multicenter bonding in π-[TCNE]22− dimer: 4c/2e, 12c/2e, or 20c/2e?

Systematic study on the structures and properties of (Ag2S)n (n = 1–8) clusters

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First principles study on the structural evolution and properties of (MCl)_n (n = 1–12, M = Cu, Ag) clusters

The nature of the multicenter bonding in π-[TCNE]₂²⁻ dimer: 4c/2e, 12c/2e, or 20c/2e?