Multimode resonances in silver nanocuboids

A rich variety of dipolar and higher order plasmon resonances have been predicted for nanoscale cubes and parallopipeds of silver, in contrast to the simple dipolar modes found on silver nanospheres or nanorods. However, in general, these multimode resonances are not readily detected in experimental colloidal ensembles, due primarily to the usual variation of size and shape of the particles obscuring or blending the individual extinction peaks. Recently, methods have been found to prepare silver parallopipeds with unprecedented shape control by nucleating the silver onto a tightly controlled suspension of gold nanorods (Okuno, Y.; Nishioka, K.; Kiya, A.; Nakashima, N.; Ishibashi, A.; Niidome, Y. Uniform and Controllable Preparation of Au-Ag Core-Shell Nanorods Using Anisotropic Silver Shell Formation on Gold Nanorods. Nanoscale 2010, 2, 1489-1493). The optical extinction spectra of suspensions of such monodisperse particles are found to contain multiple extinction peaks, which we show here to be due to the multimode resonances predicted by theoretical studies. Control of the radius of the nanoparticle edges is found to be an effective way to turn some of these modes on or off. These nanoparticles provide a flexible platform for the excitation, manipulation, and exploration of higher order plasmon resonances.     

Systems of small metal particles: Optical properties and their structure dependences

Experiments on small particles usually require samples containing large numbers of particles. The properties of such samples are determined both by the properties of the individual particle and by collective effects, if particles are packed closely together. Collective optical effects strongly depend on the topography of the samples. It is shown that they can be classified according to the effective local electromagnetic field. Recent experiments and calculations are presented for optical extinction spectra in the spectral region of plasmon polariton excitations, which clearly show the different behaviour of effective medium-like samples and of samples containing particle aggregates.     

Surface plasmon resonance of silver nanoparticles on vanadium dioxide

The localized surface plasmon resonance (SPR) spectrum of silver nanoparticles fabricated on a thermochromatic film, vanadium dioxide (VO2), is studied in this paper. Owing to the temperature-dependent dielectric function of VO2, the SPR band dramatically exhibits temperature dependence in the range of 30-80 degrees C. The peak extinction wavelength, lambda(SPR), blueshifts as temperature increases and reversibly redshifts as temperature decreases. The shift magnitude (DeltalambdaSPR) is strongly dependent on the silver mass thickness, dm; a value of 50 nm of DeltalambdaSPR is achieved for particles (mean diameter 51 nm) with dm=2 nm while a value of 250 nm is achieved for particles (mean diameter 133 nm) with dm=10 nm. Beyond the SPR band, it is interesting to find that the spectral line shape of silver particles is dominated by the imaginary part of the dielectric function of VO2. These results can be interpreted based on dynamical Maxwell-Garnett theory.     

Laser fragmentation of water-suspended gold flakes via spherical submicroparticles to fine nanoparticles

By nanosecond, 532-nm laser irradiation typically at approximately 1 J/(cm2 pulse), water-suspended thin gold flakes, 0.1-0.2-microm thick but more than 10-microm across, were efficiently fragmented in a unique two-step mode, as evidenced by the in situ extinction spectra taken as a function of the laser irradiation time. The initial main photoproducts were spherical gold particles in the submicrometer regime. Their ensuing laser fragmentation in oxygen-free water environment generated stable, negatively charged, fine nanoparticles less than 10 nm in diameter, characterized by a considerably weak and blue-shifted plasmon band. The Mie theory can reproduce these distinct spectral features of the fine nanoparticles as well as the scattering-dominated extinction spectra of the submicroparticles. The submicroparticle to nanoparticle conversion seemed most likely to be a single-pulse event, not leaving any larger intermediate nanoparticles in the suspension. Oxygen, as an effective electron acceptor, strongly affected the stability of the negatively charged nanoparticles, promoting their quasi-reversible or irreversible agglomeration. From the estimated balance between the absorbed laser energy and the energies for the relevant particles to produce a high-temperature molten state, possible fragmentation mechanisms are discussed.     

Hydrogenation of polycyclic aromatic hydrocarbons as a factor affecting the cosmic 6.2 micron emission band

While many of the characteristics of the cosmic unidentified infrared (UIR) emission bands observed for interstellar and circumstellar sources within the Milky Way and other galaxies, can be best attributed to vibrational modes of the variants of the molecular family known as polycyclic aromatic hydrocarbons (PAH), there are open questions that need to be resolved. Among them is the observed strength of the 6.2 micron (1600 cm(-1)) band relative to other strong bands, and the generally low strength for measurements in the laboratory of the 1600 cm(-1) skeletal vibration band of many specific neutral PAH molecules. Also, experiments involving laser excitation of some gas phase neutral PAH species while producing long lifetime state emission in the 3.3 micron (3000 cm(-1)) spectral region, do not result in significant 6.2 micron (1600 cm(-1)) emission. A potentially important variant of the neutral PAH species, namely hydrogenated-PAH (H(N)-PAH) which exhibit intriguing spectral correlation with interstellar and circumstellar infrared emission and the 2175 A extinction feature, may be a factor affecting the strength of 6.2 micron emission. These species are hybrids of aromatic and cycloalkane structures. Laboratory infrared absorption spectroscopy augmented by density function theory (DFT) computations of selected partially hydrogenated-PAH molecules, demonstrates enhanced 6.2 micron (1600 cm(-1)) region skeletal vibration mode strength for these molecules relative to the normal PAH form. This along with other factors such as ionization or the incorporation of nitrogen or oxygen atoms could be a reason for the strength of the cosmic 6.2 micron (1600 cm(-1)) feature.     

Investigation of the spectral,optical and surface morphology properties of the N,N′‐Dipentyl‐3,4,9,10‐perylenedicarboximide small molecule for optoelectronic applications

The spectral and optical properties of the solutions of the N,N′‐Dipentyl‐3,4,9,10‐perylenedicarboximide (PTCDI‐C5) small molecule for different molarities were investigated in detail. The significant spectral parameters such as molar/mass extinction coefficients, absorption coefficient, electric dipole line strength, and oscillator strength of the PTCDI‐C5 molecule were calculated. The absorption bands of PTCDI‐C5 show vibronic structures with seven peaks at 2.08, 2.35, 2.53, 2.70, 2.86, 3.32, and 3.86 eV, respectively. The electronic spectra of the PTCDI‐C5 can be characterized by two basic regions as visible and Soret band. Effects of the molarities on the significant many optical parameters were investigated in detail. The direct and indirect allowed optical band gaps of the PTCDI‐C5 decrease with increasing molarity. Then, surface morphology properties were investigated and calculated roughness parameters of the PTCDI‐C5 film. Finally, we discussed for optoelectronic applications of these parameters, and this study was compared with the similar and related studies in the literature. Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of particle aspect ratio on the midinfrared extinction spectra of wavelength-sized ice crystals

We have used the T-matrix method and the discrete dipole approximation to compute the midinfrared extinction cross-sections (4500-800 cm(-1)) of randomly oriented circular ice cylinders for aspect ratios extending up to 10 for oblate and down to 1/6 for prolate particle shapes. Equal-volume sphere diameters ranged from 0.1 to 10 microm for both particle classes. A high degree of particle asphericity provokes a strong distortion of the spectral habitus compared to the extinction spectrum of compactly shaped ice crystals with an aspect ratio around 1. The magnitude and the sign (increase or diminution) of the shape-related changes in both the absorption and the scattering cross-sections crucially depend on the particle size and the values for the real and imaginary part of the complex refractive index. When increasing the particle asphericity for a given equal-volume sphere diameter, the values for the overall extinction cross-sections may change in opposite directions for different parts of the spectrum. We have applied our calculations to the analysis of recent expansion cooling experiments on the formation of cirrus clouds, performed in the large coolable aerosol and cloud chamber AIDA of Forschungszentrum Karlsruhe at a temperature of 210 K. Depending on the nature of the seed particles and the temperature and relative humidity characteristics during the expansion, ice crystals of various shapes and aspect ratios could be produced. For a particular expansion experiment, using Illite mineral dust particles coated with a layer of secondary organic matter as seed aerosol, we have clearly detected the spectral signatures characteristic of strongly aspherical ice crystal habits in the recorded infrared extinction spectra. We demonstrate that the number size distributions and total number concentrations of the ice particles that were generated in this expansion run can only be accurately derived from the recorded infrared spectra when employing aspect ratios as high as 10 in the retrieval approach. Remarkably, the measured spectra could also be accurately fitted when employing an aspect ratio of 1 in the retrieval. The so-deduced ice particle number concentrations, however, exceeded the true values, determined with an optical particle counter, by more than 1 order of magnitude. Thus, the shape-induced spectral changes between the extinction spectra of platelike ice crystals of aspect ratio 10 and compactly shaped particles of aspect ratio 1 can be efficiently balanced by deforming the true number size distribution of the ice cloud. As a result of this severe size/shape ambiguity in the spectral analysis, we consider it indispensable to cross-check the infrared retrieval results of wavelength-sized ice particles with independent reference measurements of either the number size distribution or the particle morphology.     

Order-disorder transition in a quasi-two-dimensional colloidal system

A 2D colloidal system governed by repulsive dipolar forces tends to form a more ordered system when the interaction strength between the particles increases. Here we report an order-disorder transition of the colloidal system followed by chain formation upon increasing the dipolar interactions and show that the critical field scales with the density of colloids. Our system can do this by changing its dimensionality and therefore exhibits novel behavior that could help us understand colloidal ordering phenomena.     

Optical properties of fractal clusters of small metallic particles

In this paper we describe a method to calculate the optical properties of deterministic fractal clusters. Our method takes advantage of the fact that deterministic fractals can be constructed by an iterative rule. We calculate first the optical properties of a small cluster that describes one stage in the iteration. The optical properties of this cluster are then assigned to an “effective particle”. A small number of these produce the next stage in the fractal construction. We performed the calculations for metallic particles with dielectric functions described by the hydrodynamic model. Results in the dipolar and quadrupolar approximations for a cluster at the second fractal stage shows the double extinction peak often seen in experimental studies.     

Fourier-transform infrared and optical absorption spectra of 4-tricyanovinyl-N,N-diethylaniline thin films

Thin films of 4-tricyanovinyl-N,N-diethylaniline (TCVA) were prepared for the first time using thermal evaporation technique. The molecular structure and electronic transitions of TCVA films were investigated by Fourier-transform infrared (FTIR) and ultraviolet-visible (UV-vis) spectra. The observed vibrational wavenumbers in FTIR spectra were analysed and assigned to different normal modes of the molecule. UV-vis electronic absorption spectral measurements of TCVA films were analysed to obtain the electronic transitions and optical band gap (E(g)). Other important optical parameters such as molar extinction coefficient (varepsilon(molar)), the oscillator strength (f), and the electric dipole strength (q(2)) were also reported.     

Thermal dimerization kinetics of 3‐(p‐bromo‐phenyl)‐pyridazinium benzoyl methylid in solutions

3‐(p‐Bromo‐phenyl)‐pyridazinium‐benzoyl methylid (BPPBM) participates in solution at 3 + 3 dipolar thermal dimerization that can be spectrally monitored by the extinction in its visible intramolecular charge transfer (ICT) band. The attenuation of ICT band intensity shows the decrease of the BPPBM concentration with the increasing of dimer concentration. The complex kinetics of light‐assisted dimerization process was studied taking into account that the thermodynamic equilibrium is reached after more than 24 h. On the basis of general order of reaction theory, we found that the dimerization reaction must be described as a multistep mechanism. The rate constants of the dimerization reactions in ethanol (k = 0.00897 s^?1) and benzene (k = 0.00774 s^?1) solutions were correlated with the BPPBM and dimer structural features established by using the HyperChem 5.02 simulation program package. A kinetic mechanism of 3 + 3 dipolar thermal dimerization for the studied ylid is proposed. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 230–239, 2008     

Fast coagulation of gold sols. Rate constants for dimerization of nanoparticles

By using the generalized Mie theory, the extinction cross sections for dimers of 46-nm gold particles immersed in water have been calculated. It has been found that, in the region of high-energy plasmon resonance band, the maximum value of normalized extinction cross section Qext1 gradually decreases as particles approach each other. The greatest changes in Qext1 are observed when interparticle distance h decreases from 10 to 3 nm. At shorter distances, Q_ext1 weakly depends on h. At the same time, the band position varies in a complicated manner; however, at h < 2.5 nm, it coincides with that for individual particles. The revealed properties of the high-energy plasmon resonance band for dimers have been used to determine the absolute rate constant for dimerization of 46-nm gold particles k₁₁. By spectrophotometry, we have investigated salt-induced coagulation of gold sols and have measured the rates of the decrease in optical density. Experimental and calculation data allowed us to establish, at initial stages of fast coagulation, when the distance between the surfaces of 46-nm gold particles is 1.3–2.0 nm (Dolinnyi, A.I., Colloid J., 2015, vol.77, p. 600.), the average value of k₁₁ is (9.20 ± 1.34) × 10^–12 cm³/s for sols with particle concentrations of (0.4–2.6) × 10₁₀ cm^–3.     

Diffusion-limited deposition with dipolar interactions: fractal dimension and multifractal structure

Computer simulations are used to generate two-dimensional diffusion-limited deposits of dipoles. The structure of these deposits is analyzed by measuring some global quantities: the density of the deposit and the lateral correlation function at a given height, the mean height of the upper surface for a given number of deposited particles, and the interfacial width at a given height. Evidences are given that the fractal dimension of the deposits remains constant as the deposition proceeds, independently of the dipolar strength. These same deposits are used to obtain the growth probability measure through the Monte Carlo techniques. It is found that the distribution of growth probabilities obeys multifractal scaling, i.e., it can be analyzed in terms of its f(alpha) multifractal spectrum. For low dipolar strengths, the f(alpha) spectrum is similar to that of diffusion-limited aggregation. Our results suggest that for increasing the dipolar strength both the minimal local growth exponent alpha(min) and the information dimension D(1) decrease, while the fractal dimension remains the same.     

Localized surface plasmon resonances of anisotropic semiconductor nanocrystals

We demonstrate that anisotropic semiconductor nanocrystals display localized surface plasmon resonances that are dependent on the nanocrystal shape and cover a broad spectral region in the near-IR wavelengths. In-plane and out-of-plane dipolar resonances were observed for colloidal dispersions of Cu(2-x)S nanodisks, and the wavelengths of these resonances are in good agreement with calculations carried out in the electrostatic limit. The wavelength, line shape, and relative intensities of these plasmon bands can be tuned during the synthetic process by controlling the geometric aspect ratio of the disk or using a postsynthetic thermal-processing step to increase the free carrier densities.     

Optical properties of gold nanorods: DDA simulations supported by experiments

Simulations of the absorption efficiency using the discrete dipole approximation (DDA) method and taking into account the real shape of gold nanorods are reported. A dominant surface plasma band corresponding to the longitudinal resonance is observed. Its maximum position lambda(max) shifts to the red as the aspect ratio increases. The transversal dipolar and multipolar mode wavelength positions are also discussed. These data are in good agreement with previous theoretical work based on classical electrostatic predictions and assuming that gold nanorods behave as ellipsoidal particles. From the experimental point of view, good agreement with the published data for gold nanorods is obtained.     

2D-IR spectroscopy of the sulfhydryl band of cysteines in the hydrophobic core of proteins

We investigate the sulfhydryl band of cysteines as a new chromophore for two-dimensional IR (2D-IR) studies of the structure and dynamics of proteins. Cysteines can be put at almost any position in a protein by standard methods of site-directed mutagenesis and, hence, have the potential to be an extremely versatile local probe. Although being a very weak absorber in aqueous environment, the sulfhydryl group gets strongly polarized when situated in an alpha-helix inside the hydrophobic core of a protein because of a strong hydrogen bond to the backbone carbonyl group. The extinction coefficient (epsilon=150 M(-1) cm(-1)) then is sufficiently high to perform detailed 2D-IR studies even at low millimolar concentrations. Using porcine (carbonmonoxy)hemoglobin as an example, which contains two such cysteines in its wild-type form, we demonstrate that spectral diffusion deduced from the 2D-IR line shapes reports on the overall-breathing of the corresponding alpha-helix. The vibrational lifetime of the sulfhydryl group (T1 approximately 6 ps) is considerably longer than that of the much more commonly used amide I mode (approximately 1.0 ps), thereby significantly extending the time window in which spectral diffusion processes can be observed. The experiments are accompanied by molecular dynamics simulations revealing a good overall agreement.     

Absorption and scattering of light by Pt, Pd, Ag, and Au nanodisks: absolute cross sections and branching ratios

Localized surface plasmons (LSPs) of metallic nanoparticles decay either radiatively or via an electron-hole pair cascade. In this work, the authors have experimentally and theoretically explored the branching ratio of the radiative and nonradiative LSP decay channels for nanodisks of Ag, Au, Pt, and Pd, with diameters D ranging from 38 to 530 nm and height h=20 nm, supported on a fused silica substrate. The branching ratio for the two plasmon decay channels was obtained by measuring the absorption and scattering cross sections as a function of photon energy. The former was obtained from measured extinction and scattering coefficients, using an integrating sphere detector combined with particle density measurements obtained from scanning electron microscopy images of the nanoparticles. Partly angle-resolved measurements of the scattered light allowed the authors to clearly identify contributions from dipolar and higher plasmonic modes to the extinction, scattering, and absorption cross sections. Based on these experiments they find that absorption dominates the total scattering cross section in all the examined cases for small metallic nanodisks (D<100 nm). For D>100 nm absorption still dominates for Pt and Pd nanodisks, while scattering dominates for Au and Ag. A theoretical approach, where the metal disks are approximated as oblate spheroids, is used to account for the trends in the measured cross sections. The field problem is solved in the electrostatic limit. The spheroid is treated as an induced dipole for which the dipolar polarizability is calculated based on spheroid geometry and the (bulk) dielectric response function of the metal the spheroid consists of and the dielectric medium surrounding it. One might expect this model to be inappropriate for disks with D>100 nm since effects due to the retardation of the incoming field across the metallic nanodisk and contributions from higher plasmonic modes are neglected. However, this model describes quite well the energy dependence of the dipolar resonance, the full width at half maximum, and the total extinction cross section for all four metallic systems, even when 100相似文献   

Composite alignment media for the measurement of independent sets of NMR residual dipolar couplings

The measurement of independent sets of NMR residual dipolar couplings (RDCs) in multiple alignment media can provide a detailed view of biomolecular structure and dynamics, yet remains experimentally challenging. It is demonstrated here that independent sets of RDCs can be measured for ubiquitin using just a single alignment medium composed of aligned bacteriophage Pf1 particles embedded in a strained polyacrylamide gel matrix. Using this composite medium, molecular alignment can be modulated by varying the angle between the directors of ordering for the Pf1 and strained gel matrix, or by varying the ionic strength or concentration of the Pf1 particles. This approach offers significant advantages in that greater experimental control can be exercised over the acquisition of multi-alignment RDC data while a homogeneous chemical environment is maintained across all of the measured RDC data.     

Wide-field single metal nanoparticle spectroscopy for high throughput localized surface plasmon resonance sensing

Noble metal nanoparticles (mNPs) have a distinct extinction spectrum arising from their ability to support Localized Surface Plasmon Resonance (LSPR). Single-particle biosensing with LSPR is label free and offers a number of advantages, including single molecular sensitivity, multiplex detection, and in vivo quantification of chemical species etc. In this article, we introduce Single-particle LSPR Imaging (SLI), a wide-field spectral imaging method for high throughput LSPR biosensing. The SLI utilizes a transmission grating to generate the diffraction spectra from multiple mNPs, which are captured using a Charge Coupled Device (CCD). With the SLI, we are able to simultaneously image and track the spectral changes of up to 50 mNPs in a single (～1 s) exposure and yet still retain a reasonable spectral resolution for biosensing. Using the SLI, we could observe spectral shift under different local refractive index environments and demonstrate biosensing using biotin-streptavidin as a model system. To the best of our knowledge, this is the first time a transmission grating based spectral imaging approach has been used for mNPs LSPR sensing. The higher throughput LSPR sensing, offered by SLI, opens up a new possibility of performing label-free, single-molecule experiments in a high-throughput manner.