Observation of Single Molecule Plasmon-Driven Electron Transfer in Isotopically Edited 4,4′-Bipyridine Gold Nanosphere Oligomers

Sprague-Klein, Emily A.; McAnally, Michael O.; Zhdanov, Dmitry V.; Zrimsek, Alyssa B.; Apkarian, V. A.; Seideman, Tamar; Schatz, George C.; Duyne, Richard P. Van

doi:10.1021/jacs.7b08868

Cited by 64 publications

(83 citation statements)

References 92 publications

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“…The vast majority of papers concern para-nitrothiophenol -which can be reduced to paraaminothiophenol 18,34 and further dimerize to dimercaptoazobenzene 17,[35][36][37] . A number of studies describe plasmon-assisted electron transfer in biphenyl and bipirydine derivatives [38][39][40][41] . Singular reports have been published for other reactants, e. g. oxidation of phenyl isocyanide 42 , photodissociation of dimethyl disulfide 43 , demethylation of methylene blue 44 , or dehydroxylation of p-hydroxythiophenol 45 .…”

Section: Introductionmentioning

confidence: 99%

Plasmon-Driven Photocatalysis Leads to Products Known from E-beam and X-ray-Induced Surface Chemistry

et al. 2018

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Plasmonic metal nanostructures can concentrate incident optical fields in nanometersized volumes, called hot spots. This leads to enhanced optical responses of molecules in such a hot spot, but also to chemical transformations, driven by plasmon-induced hot carriers. Here, we employ tip-enhanced Raman spectroscopy (TERS) to study the mechanism of these reactions in situ, at the level of a single hot spot. Direct spectroscopic measurements reveal the energy distribution of hot electrons, as well as the temperature changes due to plasmonic heating. Therefore, charge-driven reactions can be distinguished from thermal reaction pathways. The products of the hot-carrierdriven reactions are strikingly similar to the ones known from x-ray or e-beam-induced surface chemistry, despite the >100-fold energy difference between visible and x-ray photons. Understanding the analogies between those two scenarios implies new strategies for rational design of plasmonic photocatalytic reactions and for the elimination of photoinduced damage in plasmon-enhanced spectroscopy.

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Section: Introductionmentioning

confidence: 99%

Plasmon-Driven Photocatalysis Leads to Products Known from E-beam and X-ray-Induced Surface Chemistry

et al. 2018

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“…It is known as the superatom model, which is robust and geometry distortion weakly changes the ionization potential . Another possibility might be a charge transfer that can happen during SERS measurements from excited plasmons . The roughened surface, which could be easily occurring on the surface of Au–Ag alloy, could be responsible for increasing plasmon scattering.…”

Section: Resultsmentioning

confidence: 99%

First Principles Calculations Toward Understanding SERS of 2,2′‐Bipyridyl Adsorbed on Au, Ag, and Au–Ag Nanoalloy

et al. 2018

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First principles electrodyanmics and quantum chemical simulations are performed to gain insights into the underlying mechanisms of the surface enhanced Raman spectra of 22BPY adsorbed on pure Au and Ag as well as on Au-Ag alloy nanodiscs. Experimental SERS spectra from Au and Ag nanodiscs show similar peaks, whereas those from Au-Ag alloy reveal new spectral features. The physical enhancement factors due to surface nano-texture were considered by numerical FDTD simulations of light intensity distribution for the nano-textured Au, Ag, and Au-Ag alloy and compared with experimental results. For the chemical insights of the enhancement, the DFT calculations with the dispersion interaction were performed using Au 20 , Ag 20 , and Au 10 Ag 10 clusters of a pyramidal structure for SERS modeling. Binding of 22BPY to the clusters was simulated by considering possible arrangements of vertex and planar physical as well as chemical adsorption models. The DFT results indicate that 22BPY prefers a coplanar adsorption on a (111) face with trans-conformation having close energy difference to cis-conformation. Binding to pure Au cluster is stronger than to pure Ag or Au-Ag alloy clusters and adsorption onto the alloy surface can deform the surface. The computed Raman spectra are compared with experimental data and assignments for pure Au and Ag models are well matching, indicating the need of dispersion interaction to reproduce strong Raman signal at around 800 cm -1 . This work provides insight into 3D character of SERS on nanorough surfaces due to different binding energies and bond length of nanoalloys.

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“…In order to realize enough Raman enhancement, it is crucial to design and fabricate a nanoscale confined space that can properly accommodate the molecule of interest. Recently, a single pair of Au nanosphere oligomers was designed to monitor the photoinduced reaction dynamics of an individual isotopic 4,4′‐bipyridine molecule (BPY‐h 8 or BPY‐d 8 ) from their Raman responses . The molecule was confined within the nanoscale hot spots ( Figure ), where an effective electron transfer was promoted under a pump field.…”

Section: Measurements Of Single Molecule Reactionmentioning

confidence: 99%

“…f) Top spectrum consists of neutral molecules only (black), mid‐spectrum is BPY‐d 8 anion modes, and bottom spectrum is DFT (CAM‐B3LYP) calculated BPY‐d 8 anion modes. Reproduced with permission . Copyright 2017, American Chemical Society.…”

Section: Measurements Of Single Molecule Reactionmentioning

confidence: 99%

Toward Precision Measurement and Manipulation of Single‐Molecule Reactions by a Confined Space

Qiu

Fato

Yuan

et al. 2019

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All chemical reactions can be divided into a series of single molecule reactions (SMRs), the elementary steps that involve only isomerization of, dissociation from, and addition to an individual molecule. Analyzing SMRs is of paramount importance to identify the intrinsic molecular mechanism of a complex chemical reaction, which is otherwise implausible to reveal in an ensemble fashion, owing to the significant static and dynamic heterogeneity of real‐world chemical systems. The single‐molecule measurement and manipulation methods developed recently are playing an increasingly irreplaceable role to detect and recognize short‐lived intermediates, visualize their transient existence, and determinate the kinetics and dynamics of single bond breaking and formation. Notably, none of the above SMRs characterizations can be realized without the aid of a confined space. Therefore, this Review aims to highlight the recent progress in the development of confined space enabled single‐molecule sensing, imaging, and tuning methods to study chemical reactions. Future prospects of SMRs research are also included, including a push toward the physical limit on transduction of information to signals and vice versa, transmission and recording of signals, computational modeling and simulation, and rational design of a confined space for precise SMRs.

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Observation of Single Molecule Plasmon-Driven Electron Transfer in Isotopically Edited 4,4′-Bipyridine Gold Nanosphere Oligomers

Cited by 64 publications

References 92 publications

Plasmon-Driven Photocatalysis Leads to Products Known from E-beam and X-ray-Induced Surface Chemistry

Plasmon-Driven Photocatalysis Leads to Products Known from E-beam and X-ray-Induced Surface Chemistry

First Principles Calculations Toward Understanding SERS of 2,2′‐Bipyridyl Adsorbed on Au, Ag, and Au–Ag Nanoalloy

Toward Precision Measurement and Manipulation of Single‐Molecule Reactions by a Confined Space

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