Examining the nanoworld using a molecular spectroscopist's toolbox

I will describe recent advances in understanding the influence of nanoscale structure on plasmon-mediated electron dynamics. Steady-state extinction spectra of plasmonic nanoparticle networks are accurately described using hybridization models reminiscent of molecular orbitals. We have extended these molecular-based descriptions to account for nanoparticle electron dynamics by quantifying the coherence dephasing times of collective inter-particle plasmon modes of single nanostructures. In particular, we demonstrate that interference between plasmon modes of different angular momenta leads to increased coherence times. These observations are consistent with a model based on superpositions of molecular-like electronic states. These fundamental studies are important for understanding the structure-photonic-function relationship of plasmonic nanoparticles. This is because the spectroscopically determined coherence times reflect mode quality factors, which determine achievable amplification factors of optical signals. These new insights are made possible by recent advances in single-nanoparticle/molecule spectroscopy based on interferometric nonlinear optical detection. I will describe how the generation of sequences of phase-locked femtosecond laser pulses (33mrad phase stability) and their integration to an optical microscope were critical for this research

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 nanostructure’s optical properties

Linking On-State Memory and Distributed Kinetics in Single Nanocrystal Blinking

Memory effects in single nanocrystal fluorescence blinking are investigated as a function of the on-state kinetics for CdSe/ZnS quantum dots and CdSe nanorods. The on-state duration probability distributions for single nanocrystal blinking traces are characterized by an inverse power law, which crosses over to exponential decay for long on-state durations. The correlations of subsequent on-state durations (<i>R</i>_log,on) are found to decrease for nanocrystals that display earlier crossover times and smaller power law coefficients. Specifically, <i>R</i>_log,on increases from 0.14 ± 0.02 to a saturation value of 0.44 ± 0.01 for nanocrystals with average crossover times of ∼100 ms to more than 5.0 s, respectively. The results represent the first link between memory effects and blinking kinetics and are interpreted in the framework of two competing charge trapping mechanisms. A slow fluctuation-based trapping mechanism leads to power-law-distributed on durations and significant memory effects; however, the additional contribution of an ionization-induced trapping pathway is found to induce crossover to exponential decay and decreased memory. Monte Carlo simulations of nanocrystal blinking based on the two trapping mechanisms reproduce the experimental results, suggesting that the power law component and the memory effects correlate with a fluctuation-based mechanism. This effect is found to be universal, occurring for two nanocrystal morphologies and in blinking data measured using a wide range of continuous and pulsed excitation conditions

Optical Properties and Electronic Energy Relaxation of Metallic Au₁₄₄(SR)₆₀ Nanoclusters

Electronic energy relaxation of Au₁₄₄(SR)₆₀^q ligand-protected nanoclusters, where SR = SC₆H₁₃ and <i>q</i> = −1, 0, +1, and +2, was examined using femtosecond time-resolved transient absorption spectroscopy. The observed differential transient spectra contained three distinct components: (1) transient bleaches at 525 and 600 nm, (2) broad visible excited-state absorption (ESA), and (3) stimulated emission (SE) at 670 nm. The bleach recovery kinetics depended upon the excitation pulse energy and were thus attributed to electron–phonon coupling typical of metallic nanostructures. The prominent bleach at 525 nm was assigned to a core-localized plasmon resonance (CLPR). ESA decay kinetics were oxidation-state dependent and could be described using a metal-sphere charging model. The dynamics, emission energy, and intensity of the SE peak exhibited dielectric-dependent responses indicative of Superatom charge transfer states. On the basis of these data, the Au₁₄₄(SR)₆₀ system is the smallest-known nanocluster to exhibit quantifiable electron dynamics and optical properties characteristic of metals