Manabendra Chandra

Controlled Plasmon Resonance Properties of Hollow Gold Nanosphere Aggregates

Hollow gold nanospheres (HGNs) ranging from 29.9 nm/8.5 nm (outer diameter/shell thickness) to 51.5 nm/4.5 nm and having aspect ratios spanning 3.5-11.7 were employed to investigate the ability to tailor charge oscillations of HGN aggregates by systematic variation of particle aspect ratio, interparticle gap, and nanosphere inner surface spatial separation. Altering these properties in aggregated HGNs led to control over the interparticle plasmon resonance. Thiol-mediated aggregation was accomplished using either ethanedithiol or cysteine, resulting in dimeric structures in which monomer subunits were spatially separated by <3 Å and 1.2 ± 0.7 nm, respectively. Particle dimensions and separation distances were confirmed by transmission electron microscopy. Experimental absorption spectra obtained for high-aspect ratio nanospheres dimerized using ethanedithiol exhibited an obvious blue shift of the surface plasmon resonance (SPR) relative to that observed for the native, monomeric HGN. This spectral difference likely results from a charge-transfer plasmon resonance at the dimer interface. The extent of the blue shift was dependent upon shell thickness. Dimers comprised of thin-shelled HGNs exhibited the largest shift; aggregates containing HGNs with thick shells (≥7 nm) did not display a significant SPR shift when the individual particles were in contact. By comparison, all cysteine-induced aggregates examined in this study displayed large interparticle gaps (>1 nm) and a red-shifted SPR, regardless of particle dimensions. This effect can be described fully by a surface mode coupling model. All experimental measurements were verified by finite difference time domain calculations. In addition, simulated electric field maps highlighted the importance of the inner HGN surface in the interparticle coupling mechanism. These findings, which describe structure-dependent SPR properties, may be significant for applications derived from the plasmonic nanostructure platform.

Magnetic dipolar interactions in solid gold nanosphere dimers.

We report the first observation of a magnetic dipolar contribution to the nonlinear optical (NLO) response of colloidal metal nanostructures. Second-order NLO responses from several individual solid gold nanosphere (SGN) dimers, which we prepared by a bottom-up approach, were examined using polarization-resolved second harmonic generation (SHG) spectroscopy at the single-particle level. Unambiguous circular dichroism in the SH signal was observed for most of the dimeric colloids, indicating that the plasmon field located within the interparticle gap was chiral. Detailed analysis of the polarization line shapes of the SH intensities obtained by continuous polarization variation suggested that the effect resulted from strong magnetic-dipole contributions to the nanostructures optical properties.

Optimization of nonlinear optical localization using electromagnetic surface fields (NOLES) imaging

The use of plasmon amplification of nonlinear optical wave-mixing signals to generate optical images in which the position of the scattering point source can be determined with nanometer accuracy is described. Solid gold nanosphere dimers were used as a model system for the nonlinear medium, which converted the Ti:sapphire fundamental to its second harmonic frequency. Matching the fundamental wave energy to the localized surface plasmon resonance of the electromagnetically coupled nanospheres was critical for achieving the high localization accuracy. Our technique, named Nonlinear Optical Localization using Electromagnetic Surface fields (NOLES) imaging, routinely yielded nonlinear optical images with 1-nm localization accuracy at rates ≥2 fps and can also be used as a photo-switching localization contrast method. This high level of accuracy in pinpointing the signal point source position exceeded that made possible using conventional diffraction-limited far-field methods by 160×. The NOLES technique, with its high temporal resolution and spatial accuracy that far surpass the performance typical of fluorescence-based imaging, will be relevant for imaging dynamic chemical, biological, and material environments.

Probing the Structure–Property Interplay of Plasmonic Nanoparticle Transducers Using Femtosecond Laser Spectroscopy

The characteristic feature of noble metal nanoparticles is the localized surface plasmon resonance (LSPR). Plasmon-supporting nanoparticles can function as transducers because of the LSPRs ability to amplify electromagnetic fields and its sensitivity to changes in the surrounding dielectric. The performance of these materials in transducer applications is inherently related to nanoparticle structure. This Perspective describes the use of femtosecond laser-based spectroscopies to elucidate the nanoscale structure-property interplay. First, femtosecond time-resolved transient extinction measurements that probe the LSPR following nanoparticle photoexcitation are described. These measurements illustrate how nanostructure dimensions influence sensitivity to changes in the interfacial dielectric. The combination of single-particle nonlinear optical (NLO) measurements and electron microscopy is also used to describe the symmetry of plasmon surface fields in nanoparticle assemblies. In particular, the use of continuous polarization variation-detected second-harmonic generation to describe electric and magnetic dipolar contributions to NLO properties is discussed.

Green Routes to Noble Metal Nanoparticle Synthesis

ABSTRACT In this brief review, a few green synthetic routes for the preparation of noble metal nanoparticles are presented. Many of the routes are more ‘physical’ than ‘chemical’ in their design. This article is limited to laser ablation, photochemical, sonochemical, microwave, radiolytic, and biosynthetic pathways for the production of gold, silver, and copper nanoparticles of various size and shape.

Quantum yield of Cl* (2P1/2) production in the gas phase photolysis of CCl4 in the ultraviolet

In this paper, we have probed the dynamics of chlorine atom production from the gas phase photodissociation of carbon tetrachloride at 222 and 235 nm. The quantum yield, φ* of Cl* (2P1/2) production has been determined by probing the nascent concentrations of both excited (2P1/2) and ground state (2P3/2) chlorine atoms by suitable resonance-enhanced multiphoton ionization (REMPI) detection schemes. Although at the photolysis wavelengths the absorption of carbon tetrachloride is weak, significant amounts of Cl* are produced. Surprisingly, the quantum yield of Cl* production does not follow the absorption spectrum closely, which gives rise to the possibility of an indirect dissociation mechanism present in CCl4 along with direct dissociation at these ultraviolet wavelengths