Vibrational exciton nanoimaging of phases and domains in porphyrin nanocrystals.

Much of the electronic transport, photophysical, or biological functions of molecular materials emerge from intermolecular interactions and associated nanoscale structure and morphology. However, competing phases, defects, and disorder give rise to confinement and many-body localization of the associated wavefunction, disturbing the performance of the material. Here, we employ vibrational excitons as a sensitive local probe of intermolecular coupling in hyperspectral infrared scattering scanning near-field optical microscopy (IR s-SNOM) with complementary small-angle X-ray scattering to map multiscale structure from molecular coupling to long-range order. In the model organic electronic material octaethyl porphyrin ruthenium(II) carbonyl (RuOEP), we observe the evolution of competing ordered and disordered phases, in nucleation, growth, and ripening of porphyrin nanocrystals. From measurement of vibrational exciton delocalization, we identify coexistence of ordered and disordered phases in RuOEP that extend down to the molecular scale. Even when reaching a high degree of macroscopic crystallinity, identify significant local disorder with correlation lengths of only a few nanometers. This minimally invasive approach of vibrational exciton nanospectroscopy and -imaging is generally applicable to provide the molecular-level insight into photoresponse and energy transport in organic photovoltaics, electronics, or proteins

An Alternative Representation of the Ice Canopy for Calculating Microwave Brightness Temperatures Over a Thunderstorm

Passive microwave brightness temperatures (T(B)\u27s) at 92 and 183 GHz from an aircraft thunderstorm overflight are compared with values calculated from radar-derived hydrometeor profiles and a modified proximity sounding. Two methods for modeling particles in the ice canopy are contrasted. The first is a \u27\u27traditional\u27\u27 approach employing Marshall-Palmer ice spheres. The second, or \u27\u27alternative,\u27\u27 method partitions 20% of the ice water content into a Marshall-Palmer component for graupel and hail, and 80% into a modified gamma spherical particle size distribution function representing ice crystals. Results from the alternative approach are superior to those from the traditional method in the anvil and mature convective core. In the decaying convective region, the traditional approach yields better agreement with observed magnitudes. Neither method, however, matches the geometry of the observed TB depression associated with the decaying convective core. This is likely due to the presence of graupel, which is not detected as a special signature in radar reflectivity, but does diminish T(B)\u27s through scattering. Brightness temperatures at the relatively high microwave frequencies considered are shown to be very sensitive to the ice-particle size distribution

3-D Tracking and Visualization of Hundreds of Pt-Co Fuel Cell Nanocatalysts During Electrochemical Aging

We present an electron tomography method that allows for the identification of hundreds of electrocatalyst nanoparticles with one-to-one correspondence before and after electrochemical aging. This method allows us to track, in three-dimensions (3-D), the trajectories and morphologies of each Pt-Co nanocatalyst on a fuel cell carbon support. The use of atomic-scale electron energy loss spectroscopic imaging enables the correlation of performance degradation of the catalyst with changes in particle/inter-particle morphologies, particle-support interactions and the near-surface chemical composition. We found that, aging of the catalysts under normal fuel cell operating conditions (potential scans from +0.6 V to +1.0 V for 30,000 cycles) gives rise to coarsening of the nanoparticles, mainly through coalescence, which in turn leads to the loss of performance. The observed coalescence events were found to be the result of nanoparticle migration on the carbon support during potential cycling. This method provides detailed insights into how nanocatalyst degradation occurs in proton exchange membrane fuel cells (PEMFCs), and suggests that minimization of particle movement can potentially slow down the coarsening of the particles, and the corresponding performance degradation.Comment: Nano Letters, accepte

Mapping local optical densities of states in silicon photonic structures with nanoscale electron spectroscopy

Relativistic electrons in a structured medium generate radiative losses such as Cherenkov and transition radiation that act as a virtual light source, coupling to the photonic densities of states. The effect is most pronounced when the imaginary part of the dielectric function is zero, a regime where in a non-retarded treatment no loss or coupling can occur. Maps of the resultant energy losses as a sub-5nm electron probe scans across finite waveguide structures reveal spatial distributions of optical modes in a spectral domain ranging from near-infrared to far ultraviolet.Comment: 18 pages, 4 figure

Broadband Infrared Vibrational Nano-spectroscopy Using Thermal Blackbody Radiation

Infrared vibrational nano-spectroscopy based on scattering scanning near-field optical microscopy (s-SNOM) provides intrinsic chemical specificity with nanometer spatial resolution. Here we use incoherent infrared radiation from a 1400 K thermal blackbody emitter for broadband infrared (IR) nano-spectroscopy. With optimized interferometric heterodyne signal amplification we achieve few-monolayer sensitivity in phonon polariton spectroscopy and attomolar molecular vibrational spectroscopy. Near-field localization and nanoscale spatial resolution is demonstrated in imaging flakes of hexagonal boron nitride (hBN) and determination of its phonon polariton dispersion relation. The signal-to-noise ratio calculations and analysis for different samples and illumination sources provide a reference for irradiance requirements and the attainable near-field signal levels in s-SNOM in general. The use of a thermal emitter as an IR source thus opens s-SNOM for routine chemical FTIR nano-spectroscopy

Interacting electrons in disordered potentials: Conductance versus persistent currents

An expression for the conductance of interacting electrons in the diffusive regime as a function of the ensemble averaged persistent current and the compressibility of the system is presented. This expression involves only ground-state properties of the system. The different dependencies of the conductance and persistent current on the electron-electron interaction strength becomes apparent. The conductance and persistent current of a small system of interacting electrons are calculated numerically and their variation with the strength of the interaction is compared. It is found that while the persistent current is enhanced by interactions, the conductance is suppressed.Comment: REVTeX, 4 pages, 3 figures, all uuencoded, accepted for publication in PR