Quantized Evolution of the Plasmonic Response in a Stretched Nanorod

Rossi, Tuomas P.; Zugarramurdi, A.; Puska, Martti J.; Nieminen, Risto M.

doi:10.1103/physrevlett.115.236804

Cited by 55 publications

(74 citation statements)

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“…Previous studies of linked NPs have shown that a tunneling charge transfer plasmon (tCTP) can form between NPs when they are connected with a molecular linker or similar structure. [44][45][46][47][48] This mode typically exists together with the BDP mode, it is red-shifted with respect to the BDP mode, and it depends sensitively on the tunneling properties of the NP -molecule -NP junction. Moreover, tunneling through molecular states allows coupling over much longer distances than the normal charge transfer plasmon (CTP), that happens only over very short (< 1 nm) insulating gaps and causes blue-shift instead of red-shift 44,49,50 Simulations of a simple two-level system between plasmonic NPs have showed that tCTP mode forms when a molecular state localized on the linker is near the Fermi level of the combined system.…”

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

Covalently linked multimers of gold nanoclusters Au₁₀₂(p-MBA)₄₄and Au_∼250(p-MBA)_n

et al. 2016

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We present the synthesis, separation, and characterization of covalently-bound multimers of paramercaptobenzoic acid (p-MBA) protected gold nanoclusters. The multimers were synthesized by performing a ligand-exchange reaction of a pre-characterized Au 102 (p-MBA) 44 nanocluster with biphenyl-4,4'dithiol (BPDT). The reaction products were separated using gel electrophoresis yielding several distinct bands. The bands were analyzed by transmission electron microscopy (TEM) revealing monomer, dimer, and trimer fractions of the nanocluster. TEM analysis of dimers in combination with molecular dynamics simulations suggest that the nanoclusters are covalently bound via a disulfide bridge between BPDT molecules. The linking chemistry is not specific to Au 102 (p-MBA) 44 . The same approach yields multimers also for a larger monodisperse p-MBA-protected cluster of approximately 250 gold atoms, Au ∼250 (p-MBA) n . While the Au 102 (p-MBA) 44 is not plasmonic, the Au ∼250 (p-MBA) n nanocluster supports localized surface plasmon resonance (LSPR) at 530 nm. Multimers of the Au ∼250 (p-MBA) n exhibit additional transitions in their UV-vis spectrum at 630 nm and 810 nm, indicating the presence of hybridized LSPR modes. Well-defined structures and relatively small sizes make these systems excellent candidates for connecting ab initio theoretical studies and experimental quantum plasmonics. Moreover, our work opens new possibilities in the controlled synthesis of advanced monodisperse nanocluster superstructures. † Electronic supplementary information (ESI) available: Details of syntheses and purification; additional images of PAGE runs; mass spectrum of Au 102 ( p-MBA) 44 ; 1 H NMR spectra of clusters; TEM analysis of cluster sizes; additional TEM images; core-to-core distance and angle distributions from simulations; additional multimer size statistics; additional UV-vis spectra for Au ∼250 ( p-MBA) n multimers and aggregates. See

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Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

Covalently linked multimers of gold nanoclusters Au₁₀₂(p-MBA)₄₄and Au_∼250(p-MBA)_n

et al. 2016

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“…They are also one of the simplest anisotropic structures that lead to strong and tunable resonances. Single-atom-thick chains, which have become a standard "workhorse" of quantum plasmonics [18][19][20]23,[32][33][34][35], represent the ultimate aspect ratio limit of nanorods. Their small size could lead to added tunability and novel quantum plasmonic behavior as well as aid in our understanding of how plasmons arise in larger systems within a quantum picture.…”

Section: Introductionmentioning

confidence: 99%

Quantum plasmonic nanoantennas

2017

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We study plasmonic excitations in the limit of few electrons, in one-atom-thick sodium chains. We compare the excitations to classical localized plasmon modes, and we find for the longitudinal mode a quantum-classical transition around 10 atoms. The transverse mode appears at much higher energies than predicted classically for all chain lengths. The electric field enhancement is also considered, which is made possible by considering the effects of electron-phonon coupling on the broadening of the electronic spectra. Large field enhancements are possible on the molecular level allowing us to consider the validity of using molecules as the ultimate small size limit of plasmonic antennas. Additionally, we consider the case of a dimer system of two sodium chains, where the gap can be considered as a picocavity, and we analyze the charge-transfer states and their dependence on the gap size as well as chain size. Our results and methods are useful for understanding and developing ultrasmall, tunable, and novel plasmonic devices that utilize quantum effects that could have applications in quantum optics, quantum metamaterials, cavity-quantum electrodynamics, and controlling chemical reactions, as well as deepening our understanding of localized plasmons in low-dimensional molecular systems.

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“…Coinage metal dimers offer a dramatic enhancement of the induced optical field at the point of closest proximity, showing shifts of plasmon resonances toward the infrared with modes appearing and disappearing in the near‐touching limit . Several theoretical papers study the optical response as two nanorod ends approach and form atom‐sized necks across the junction . Particles in the near‐touching limit depend sensitively on transport properties across the subnanometric metallic gaps and a more detailed discussion is presented below.…”

Section: Introductionmentioning

confidence: 99%

Nanoscale Plasmon‐Enhanced Spectroscopy in Memristive Switches

Martino

Tappertzhofen

Hofmann

et al. 2016

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Resistive switching memories are nonvolatile memory cells based on nano‐ionic redox processes and offer prospects for high scalability, ultrafast write and read access, and low power consumption. In two‐terminal cation based devices a nanoscale filament is formed in a switching material by metal ion migration from the anode to the cathode. However, the filament growth and dissolution mechanisms and the dynamics involved are still open questions, restricting device optimization. Here, a spectroscopic technique to optically characterize in situ the resistive switching effect is presented. Resistive switches arranged in a nanoparticle‐on‐mirror geometry are developed, exploiting the high sensitivity to morphological changes occurring in the tightly confined plasmonic hotspot within the switching material. The focus is on electrochemical metallization and the optical signatures detected over many cycles indicate incomplete removal of metal particles from the filament upon RESET and suggest that the filament can nucleate from different positions from cycle to cycle. The technique here is nondestructive and the measurements can be easily performed in tunable ambient conditions and with realistic cell geometries.

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Quantized Evolution of the Plasmonic Response in a Stretched Nanorod

Cited by 55 publications

References 59 publications

Covalently linked multimers of gold nanoclusters Au₁₀₂(p-MBA)₄₄and Au_∼250(p-MBA)_n

Covalently linked multimers of gold nanoclusters Au₁₀₂(p-MBA)₄₄and Au_∼250(p-MBA)_n

Quantum plasmonic nanoantennas

Nanoscale Plasmon‐Enhanced Spectroscopy in Memristive Switches

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Quantized Evolution of the Plasmonic Response in a Stretched Nanorod

Cited by 55 publications

References 59 publications

Covalently linked multimers of gold nanoclusters Au102(p-MBA)44and Au∼250(p-MBA)n

Covalently linked multimers of gold nanoclusters Au102(p-MBA)44and Au∼250(p-MBA)n

Quantum plasmonic nanoantennas

Nanoscale Plasmon‐Enhanced Spectroscopy in Memristive Switches

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Product

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Covalently linked multimers of gold nanoclusters Au₁₀₂(p-MBA)₄₄and Au_∼250(p-MBA)_n

Covalently linked multimers of gold nanoclusters Au₁₀₂(p-MBA)₄₄and Au_∼250(p-MBA)_n