showing 13 related works from this author
Cubic aromaticity in ligand-stabilized doped Au superatoms
2021
The magnetic response of valence electrons in doped gold-based [M@Au8L8]q superatoms (M = Pd, Pt, Ag, Au, Cd, Hg, Ir, and Rh; L = PPh3; and q = 0, +1, +2) is studied by calculating the gauge including magnetically induced currents (GIMIC) in the framework of the auxiliary density functional theory. The studied systems include 24 different combinations of the dopant, total cluster charge, and cluster structure (cubic-like or oblate). The magnetically induced currents (both diatropic and paratropic) are shown to be sensitive to the atomic structure of clusters, the number of superatomic electrons, and the chemical nature of the dopant metal. Among the cubic-like structures, the strongest arom…
Solubility-Driven Isolation of a Metastable Nonagold Cluster with Body-Centered Cubic Structure.
2020
The conventional synthetic methodology of atomically precise gold nanoclusters using reduction in solutions offers only thermodynamically most stable nanoclusters. We report herein a solubility‐driven isolation strategy to access the synthesis of a metastable gold cluster. The cluster, with the composition of [Au 9 (PPh 3 ) 8 ] + ( 1 ), displays an unusual, nearly perfect body‐centered‐cubic (bcc) structure. As revealed by ESI‐MS and UV/Vis measurement, the cluster is metastable in solution and converts to the well‐known [Au 11 (PPh 3 ) 8 Cl 2 ] + ( 2 ) within just 90 min. DFT calculations revealed that while both 1 and 2 are eight‐electron superatoms, there is a driving force to convert 1 …
Solvent-mediated assembly of atom-precise gold–silver nanoclusters to semiconducting one-dimensional materials
2020
Bottom-up design of functional device components based on nanometer-sized building blocks relies on accurate control of their self-assembly behavior. Atom-precise metal nanoclusters are well-characterizable building blocks for designing tunable nanomaterials, but it has been challenging to achieve directed assembly to macroscopic functional cluster-based materials with highly anisotropic properties. Here, we discover a solvent-mediated assembly of 34-atom intermetallic gold–silver clusters protected by 20 1-ethynyladamantanes into 1D polymers with Ag–Au–Ag bonds between neighboring clusters as shown directly by the atomic structure from single-crystal X-ray diffraction analysis. Density fun…
Thiol-Stabilized Atomically Precise, Superatomic Silver Nanoparticles for Catalyzing Cycloisomerization of Alkynyl Amines
2018
Abstract Both the electronic and surface structures of metal nanomaterials play critical roles in determining their chemical properties. However, the non-molecular nature of conventional nanoparticles makes it extremely challenging to understand the molecular mechanism behind many of their unique electronic and surface properties. In this work, we report the synthesis, molecular and electronic structures of an atomically precise nanoparticle, [Ag206L72]q (L = thiolate, halide; q = charge). With a four-shell Ag7@Ag32@Ag77@Ag90 Ino-decahedral structure having a nearly perfect D5h symmetry, the metal core of the nanoparticle is co-stabilized by 68 thiolate and 4 halide ligands. Both electroche…
Charge Transfer Plasmons in Dimeric Electron Clusters
2020
The tunability of the optical response of dimers of metal clusters and nanoparticles makes them ideal for many applications from sensing and imaging to inducing chemical reactions. We have studied charge transfer plasmons in separate and linked dimers of closed-shell electron clusters of 8 and 138 electrons using time-dependent density functional theory. The simple model clusters enable the systematic study of the charge transfer phenomenon from the electronic perspective. To identify the charge transfer plasmons, we have developed an index, the Charge Transfer Ratio, for quantifying the charge transfer nature of the excitations. In addition, we analyze the induced transition density and th…
Analysis of the plasmonic excitations in assemblies of three-dimensional electron clusters
2020
In the quest to built novel metamaterials with unique optical properties, three-dimensional assemblies of metal clusters and nanoparticles are gathering significant attention. Organized geometries, such as tetrahedra and icosahedra, can be built, for example, by using DNA strands or virus capsids as templates. Here we use the jellium model and time-dependent density functional theory to study the plasmonic resonances in different arrangements of eight-electron clusters from the electronic perspective. A charge transfer ratio index based on the induced transition densities is used to quantify the charge transfer nature of the excitations at different energies. We vary the size, shape, and in…
Analysis of Localized Surface Plasmon Resonances in Spherical Jellium Clusters and Their Assemblies
2017
Due to multiple possible applications of physico-chemical properties of plasmonic metal nanoparticles and particle systems, there is high interest to understand the mechanisms that underlie the birth of localized surface plasmon resonance (LSPR). Here we studied the birth of the LSPR in spherical jellium clusters with the density of sodium and with 8, 20, 34, 40, 58, 92, 138, and 186 electrons, by using the linear response time-dependent density functional theory (lr-TDDFT). The coupling of the individual plasmon resonances in dimer, trimer, tetramer, and hexamer cluster assemblies consisting of the 8-electron cluster was also studied. The Kohn-Sham electron-hole transitions contributing to…
Optical properties of small, spherical sodium clusters and dimers calculated using the jellium model and lr-TDDFT
2016
Magnetically induced currents and aromaticity in ligand-stabilized Au and AuPt superatoms
2021
Understanding magnetically induced currents (MICs) in aromatic or metallic nanostructures is crucial for interpreting local magnetic shielding and NMR data. Direct measurements of the induced currents have been successful only in a few planar molecules but their indirect effects are seen in NMR shifts of probe nuclei. Here, we have implemented a numerically efficient method to calculate gauge-including MICs in the formalism of auxiliary density functional theory. We analyze the currents in two experimentally synthesized gold-based, hydrogen-containing ligand-stabilized nanoclusters [HAu9(PPh3)8]2+ and [PtHAu8(PPh3)8]+. Both clusters have a similar octet configuration of Au(6s)-derived deloc…
CCDC 1962411: Experimental Crystal Structure Determination
2020
Related Article: Peng Yuan, Ruihua Zhang, Elli Selenius, Pengpeng Ruan, Yangrong Yao, Yang Zhou, Sami Malola, Hannu Häkkinen, Boon K. Teo, Yang Cao, Nanfeng Zheng|2020|Nat.Commun.|11|2229|doi:10.1038/s41467-020-16062-6
CCDC 1962412: Experimental Crystal Structure Determination
2020
Related Article: Peng Yuan, Ruihua Zhang, Elli Selenius, Pengpeng Ruan, Yangrong Yao, Yang Zhou, Sami Malola, Hannu Häkkinen, Boon K. Teo, Yang Cao, Nanfeng Zheng|2020|Nat.Commun.|11|2229|doi:10.1038/s41467-020-16062-6
CCDC 1811378: Experimental Crystal Structure Determination
2018
Related Article: Juanzhu Yan, Jun Zhang, Xumao Chen, Sami Malola, Bo Zhou, Elli Selenius, Xiaomin Zhang, Peng Yuan, Guocheng Deng, Kunlong Liu, Haifeng Su, Boon K. Teo, Hannu Häkkinen, Lansun Zheng, Nanfeng Zheng|2018|National Science Review|5|694|doi:10.1093/nsr/nwy034
CCDC 1967410: Experimental Crystal Structure Determination
2020
Related Article: Hui Shen, Elli Selenius, Pengpeng Ruan, Xihua Li, Peng Yuan, Omar Lopez-Estrada, Sami Malola, Shuichao Lin, Boon K. Teo, Hannu Häkkinen, Nanfeng Zheng|2020|Chem.-Eur.J.|26|8465|doi:10.1002/chem.202001753