KEYWORDS (Word Style "BG_Keywords"). If you are submitting your paper to a journal that requires keywords, provide significant keywords to aid the reader in literature retrieval.In this work, we present a novel technique to directly measure the phase shift of the optical signal scattered by single plasmonic nanoparticles in a diffraction-limited laser focus. We accomplish this by equipping an inverted confocal microscope with a Michelson interferometer and scanning single nanoparticles through the focal volume while recording interferograms of the scattered and a reference wave for each pixel. For the experiments, lithographically prepared gold nanorods where used, since their plasmon resonances can be controlled via their aspect ratio. We have developed a theoretical model for image formation in confocal scattering microscopy for nanoparticles considerably smaller than the diffraction limited focus We show that the phase shift observed for particles with different longitudinal particle plasmon resonances can be well explained by the harmonic oscillator model. The direct measurement of the phase shift can further improve the understanding of the elastic scattering of individual gold nanoparticles with respect to their plasmonic properties.

SummaryThe ring opening of the Dewar form of 1,2-dihydro-1,2-azaborine, 2-aza-3-borabicyclo[2.2.0]hex-5-ene (3) is investigated by theoretical methods by using multiconfiguration SCF (CASSCF) and coupled cluster theory [CCSD(T)] with basis sets up to polarised quadruple-zeta quality. The title compound was previously reported to form photochemically in cryogenic noble gas matrices from 1,2-dihydro-1,2-azaborine (4). Four reaction paths for the thermal ring opening of 3 to 4 could be identified. These are the conventional disrotatory and conrotatory electrocyclic ring-opening pathways where the BN unit is only a bystander. Two more favourable paths are stepwise and involve 1,3-boron–carbon interactions. The lowest energy barrier for the isomerisation reaction, 22 kcal mol−1, should be high enough for an experimental observation in solution. However, in solution the dimerisation of 3 is computed to have a very low barrier (3 kcal mol−1), and thus 3 is expected to be a short-lived reactive intermediate.

Hypericin can be found in nature in Hypericum perforatum (St. John's Wort) and has become subject of intense biochemical research. Studies report of antidepressive, antineoplastic, antitumor and antiviral activity of hypericin. Among the variety of potential applications hypericin can be used as photosensitizer in photodynamic therapy (PDT), where it is brought into cancer cells and produces singlet oxygen upon irradiation with a suitable light source. Therefore, the photophysical properties of hypericin are crucial for a successful application in a medical treatment. Here, we present the first single molecule optical spectroscopy study of hypericin. Its photostability is large enough to obtain single molecule fluorescence, surface enhanced Raman spectra (SERS), fluorescence lifetime, antibunching and blinking dynamics. Embedding hypericin in a PVA matrix changes the blinking dynamics, reduces the fluorescence lifetime and increases the photostability. Single molecule SERS spectra show both the neutral and deprotonated form of hypericin and exhibit sudden spectral changes, which can be associated with a reorientation of the single molecule with respect to the surface.

AbstractMechanically controllable break junctions are one suitable approach to generate atomic point contacts and ultrasmall and controllable gaps between two metal contacts. For constant bias voltages, the tunneling current can be used as a ruler to evaluate the distance between the contacts in the sub-1-nm regime and with sub-Å precision. This ruler can be used to measure the distance between two plasmonic nanostructures located at the designated breaking point of the break junction. In this work, an experimental setup together with suitable nanofabricated break junctions is developed that enables us to perform simultaneous gap-dependent optical and electrical characterization of coupled plasmonic particles, more specifically bowtie antennas in the highly interesting gap range from few nanometers down to zero gap width. The plasmonic break junction experiment is performed in the focus of a confocal microscope. Confocal scanning images and current measurements are simultaneously recorded and exhibit an increased current when the laser is focused in the proximity of the junction. This setup offers a flexible platform for further correlated optoelectronic investigations of coupled antennas or junctions bridged by nanomaterials.

The chemical synthesis of polysiloxanes from monomeric starting materials involves a series of hydrolysis, condensation and modification reactions with complex monomeric and oligomeric reaction mixtures. Real-time monitoring and precise process control of the synthesis process is of great importance to ensure reproducible intermediates and products and can readily be performed by optical spectroscopy. In chemical reactions involving rapid and simultaneous functional group transformations and complex reaction mixtures, however, the spectroscopic signals are often ambiguous due to overlapping bands, shifting peaks and changing baselines. The univariate analysis of individual absorbance signals is hence often only of limited use. In contrast, batch modelling based on the multivariate analysis of the time course of principal components (PCs) derived from the reaction spectra provides a more efficient tool for real-time monitoring. In batch modelling, not only single absorbance bands are used but information over a broad range of wavelengths is extracted from the evolving spectral fingerprints and used for analysis. Thereby, process control can be based on numerous chemical and morphological changes taking place during synthesis. “Bad” (or abnormal) batches can quickly be distinguished from “normal” ones by comparing the respective reaction trajectories in real time. In this work, FTIR spectroscopy was combined with multivariate data analysis for the in-line process characterization and batch modelling of polysiloxane formation. The synthesis was conducted under different starting conditions using various reactant concentrations. The complex spectral information was evaluated using chemometrics (principal component analysis, PCA). Specific spectral features at different stages of the reaction were assigned to the corresponding reaction steps. Reaction trajectories were derived based on batch modelling using a wide range of wavelengths. Subsequently, complexity was reduced again to the most relevant absorbance signals in order to derive a concept for a low-cost process spectroscopic set-up which could be used for real-time process monitoring and reaction control.

Surface charging effects at metal−molecule interfaces, for example, charge transfer, charge transport, charge injection, and so on, have a strong impact on the performance of organic electronics. Only having molecules bound or adsorbed on different metals results in a doping-like behavior at the interface by the different work functions of the metals and creates hybrid surface states, which strongly affect the efficiencies. With the ongoing downsizing and thinning of the organic components, the impact of the interface will even further increase. However, most of the investigations only monitor the interface without the additional charging effects from applying a voltage to the interface. In this work we present a spectroscopic approach based on tip-enhanced Raman spectroscopy (TERS) to study metal−molecule interfaces with an applied voltage simulating the electric field strength in real devices. We monitor how an intrinsic inductive effect of partial functional groups in molecules can shift the molecular electron density (ED) distribution when a bias voltage is applied. Therefore, we choose two molecules as model systems, which are similar in size and binding condition to a smooth gold surface, but with different electronic structure. By placing the tip 1 nm over the molecular surface at a fixed position and changing the applied bias voltage, we record electric-field-dependent tip-enhanced Raman spectra. Specific vibrational bands exhibit voltage-dependent intensity changes related to the shift of the local ED inside the molecules. We believe this experiment is valuable to gain deeper insights into charged metal−molecule interfaces.

The plasmon ruler has drawn substantial attention for measuring small separations between two plasmonic nanoparticles (NPs), which can be as sensitive as to observe the bending of DNA. Usually, the plasmon ruler is based on the spectral shift of the localized surface plasmon resonance (LSPR) caused by the distance-dependent dipole−dipole coupling between two plasmonic NPs. Here, we present an approach to the plasmon ruler by detecting the phase of the scattered light. We have developed a combination of a confocal microscope and a Michelson interferometer, which allows us to measure the phase change caused by a single nanoparticle in a diffraction-limited focal volume. The plasmon ruler is realized by a gold nanoparticle dimer (GND) deposited on a flexible polydimethylsiloxane substrate, where the same GND can be investigated with variable gaps by applying strain by stretching of the substrate. In this experimental configuration, the GND is located at a low reflecting interface leading to a large phase difference of more than 100°relative to the substrate, which allows us to easily detect a single GND. Interestingly, an increase of the gap by 11 nm leads to a large phase shift of 94°, even though there is only a 11 nm spectral shift of the LSPR. We find that both the spectral and phase shifts have the same r −3 dependence on the particle gap, which is expected for pure dipole−dipole coupling.

In this review, we focus on the experimental demonstration of enhanced emission from single plasmonic tunneling junctions consisting of coupled nano antennas or noble metal tips on metallic substrates in scanning tunneling microscopy. Electromagnetic coupling between resonant plasmonic oscillations of two closely spaced noble metal particles leads to a strongly enhanced optical near field in the gap between. Electron beam lithography or wet chemical synthesis enables accurate control of the shape, aspect ratio, and gap size of the structures, which determines the spectral shape, position, and width of the plasmonic resonances. Many emerging nano-photonic technologies depend on the careful control of such localized resonances, including optical nano antennas for high-sensitivity sensors, nanoscale control of active devices, and improved photovoltaic devices. The results discussed here show how optical enhancement inside the plasmonic cavity can be further increased by a stronger localization via tunneling. Inelastic electron tunneling emission from a plasmonic junction allows for new analytical applications. Furthermore, the reviewed concepts represent the basis for novel ultra-small, fast, optically, and electronically switchable devices and could find applications in high-speed signal processing and optical telecommunications.