In Search of the Quantum-Electronic Origin of Color Change: Elucidation of the Subtle Effects of Alloying with Copper on ≈1.8 nm Gold Nanoclusters

Sinha-Roy, Rajarshi; López-Lozano, Xóchitl; Whetten, Robert L.; Garcı́a-González, P.; Weissker, Hans‐Christian

doi:10.1021/acs.jpcc.7b00581

Cited by 11 publications

(12 citation statements)

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“…From an ab initio perspective, timedependent density-functional theory (TDDFT) 33 is the method of choice to study collective excitations in metallic nanostructures. 21,29,[34][35][36][37][38] In TDDFT, the time evolution of the density of the many-electron system is obtained from a fictitious non-interacting one, the timedependent Kohn-Sham system, under the action of an effective time-dependent potential.…”

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confidence: 99%

Classical and ab Initio Plasmonics Meet at Sub-nanometric Noble Metal Rods

et al. 2017

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Applications of noble metal clusters and nanoparticles in different size ranges abound, from a couple of atoms through mesoscopic sizes. Classical electromagnetics calculations are now employed on smaller and smaller sizes, creating an effervescent dynamic in fields such as plasmonics and approaching the tiny sizes where quantum effects and the atomistic structure of matter play predominant roles. Nonetheless, explicit demonstrations of their merits and limitations are rare. Here we study the optical absorption of subnanometric elongated coinage-metal particles using ab initio and classical electromagnetics methods. The comparison between both approaches reveals that the classical plasmonic frequencies are in astonishing agreement with those predicted by ab initio theory for atomistic three-dimensional rods and quasi-one-dimensional chains, as long as collective surface-plasmon resonances lie far below the onset of d-electron excitations. The physical origin of this striking agreement is clarified through the analysis of the resonant induced electron densities and with the aid of model calculations for a purely one-dimensional system of electrons. Furthermore, we show that even when plasmonic/collective and electron−hole excitations are strongly coupled, the classical description accounts rather well for the spectral average of the corresponding quantum hybrid excitations. Our theoretical findings demonstrate that classical optics is surprisingly accurate in describing localized surface plasmon resonances even for angstrom-sized systems, provided the geometrical modeling of the atomistic structures is properly defined.

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confidence: 99%

Classical and ab Initio Plasmonics Meet at Sub-nanometric Noble Metal Rods

et al. 2017

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“…Analysis of ligand and alloying (Cu for Au replacement) effects have been given elsewhere. 34,36,37 Shown is a comparison between spectra calculated by the real-time TD-DFT method assuming (red) the I-symmetrized structure with 60 methane-thiolate (CH3S-) ligands, versus (black) the experimental structure that has 60 benzyl-thiolate ligands (PhCH2S-).…”

Section: Optical Spectra Sensitivity To Structure and Symmetry Low-tmentioning

confidence: 99%

Chiral-Icosahedral (I) Symmetry in Ubiquitous Metallic Cluster Compounds (145A,60X): Structure and Bonding Principles

et al. 2019

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CONSPECTUS: There exists a special kind of perfectionin symmetry, simplicity, and stabilityattainable for structures generated from precisely 60 ligands (all of a single type) that protect 145 metal-atom sites. The symmetry in question is icosahedral (I h ), generally, and chiral icosahedral (I) in particular. A 60-fold equivalence of the ligands is the smallest number to allow this kind of perfection. Known cluster compounds that approximate this structural ideal include palladium-carbonyls, I h -Pd 145 (CO) 60 ; gold-thiolates, I-Au 144 (SR) 60 ; and gold-alkynyls, I-Au 144 (C 2 R) 60 . Many other variants are suspected. The Pd 145 compound established the basic achiral structure-type. However, the Au 144 -thiolate archetype is prominent, historically in its abundance and ease of preparation and handling, in its proliferation in many laboratories and application areas, and ultimately in the intrinsic chirality of its geometrical structure and organization of its bonding network or connectivity. As discovered by mass spectrometry (the "30-k anomaly") in 1995, it appeared as a broad single peak, as solitary and symmetrical as Mount Fuji, centered near 30 kDa (∼150 Au atoms), provoking these thoughts: Surely this phenomenon requires a unique explanation. It appears to be the Buckminsterfullerene (carbon-60) of gold-cluster chemistry. Herein we provide an elementary account of the unexpected discovery, in which the Pd 145 -structure played a critical role, that led to the identification and prediction, in 2008, of a fascinating new molecular structure-type, evidently the first one of chiral icosahedral symmetry. Rigorous confirmation of this prediction occurred in early spring 2018, when two single-crystal X-ray crystallography reports were submitted, each one distinguishing both enantiomeric structures and noting profound chirality for the surface (ligand) layer. The emphasis here is on the structure and bonding principles and how these have been elucidated. Our aim has been to present this story in simplest terms, consistent with the radical simplicity of the structure itself. Because it combines intrinsic profound chirality, at several levels, with the highest possible symmetry-type (icosahedral), the structure may attract broader interest also from educators, especially if studied in tandem with the analysis of hollow (shell) metallic systems that exhibit the same chirality and symmetry. Because the shortest (stiffest) bonds follow the chiral 3-way weave pattern of the traditional South-Asian reed football, this cultural artifact may be used to introduce chiral-icosahedral symmetry in a pleasant and memorable way. One may also appreciate easily the bonding and excitations in I-symmetry metallic nanostructures via the golden fullerenes, that is, the proposed hollow Au 60 , 72 spheres. Beyond any aesthetic or pedagogical value, we aim that our Account may provide a firm foundation upon which others may address open questions and the opportunities they present. This Account can scarcely hint at the prospects for...

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“…In recent years, the development of nanomaterials, especially nanoclusters [28, 29], has enriched the research of nanomaterials science. The preparation of related functional materials [30, 31] using gold nanoparticles has received much attention for their ease of preparation and modification, high density, and dielectric constant. Gold nanoclusters are widely used in many fields such as fluorescence detection [32–34], biomarkers [35, 36], and catalysis [37, 38] because of their strong fluorescence stability, good biocompatibility, low cytotoxicity, and large Stoke's shift.…”

Section: Introductionmentioning

confidence: 99%

Recent Progress on Gold-Nanocluster-Based Fluorescent Probe for Environmental Analysis and Biological Sensing

Liu

Tang

Yang

et al. 2019

Journal of Analytical Methods in Chemistry

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Gold nanoclusters (AuNCs) are one of metal nanoclusters, which play a pivotal role in the recent advances in the research of fluorescent probes for their fluorescence effect. They are favored by most researchers due to their strong stability in fluorescence and adjustability in fluorescence wavelength when compared to traditional organic fluorescent dyes. In this review, we introduce various synthesis strategies of gold-nanocluster-based fluorescent probes and summarize their application for environmental analysis and biological sensing. The use of gold-nanocluster-based fluorescent probes for the analysis of heavy metals and inorganic and organic pollutants is covered in the environmental analysis while biological labeling, imaging, and detection are presented in biological sensing.

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In Search of the Quantum-Electronic Origin of Color Change: Elucidation of the Subtle Effects of Alloying with Copper on ≈1.8 nm Gold Nanoclusters

Abstract: Experiments on the Au 144 (SR) 60 class of cluster compounds have demonstrated the emergence of an absorption peak at 550 nm (2.25 eV) upon adding copper to the pure Au samples; in some cases, as little as one Cu atom seems to have this effect

Cited by 11 publications

References 51 publications

Classical and ab Initio Plasmonics Meet at Sub-nanometric Noble Metal Rods

Classical and ab Initio Plasmonics Meet at Sub-nanometric Noble Metal Rods

Chiral-Icosahedral (I) Symmetry in Ubiquitous Metallic Cluster Compounds (145A,60X): Structure and Bonding Principles

Recent Progress on Gold-Nanocluster-Based Fluorescent Probe for Environmental Analysis and Biological Sensing

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