Influence of bulky substituents on single-molecule SERS sensitivity.

The surface-enhanced Raman spectroscopy (SERS) detection limit strongly depends on the molecular structure, which we demonstrate for a family of tert-butyl-substituted porphycenes. Even though the investigated species present very similar photophysical properties, the ratio between the SERS signal and fluorescence background depends on the number of bulky tert-butyl groups. Moreover, the probability of single molecule detection systematically drops with the number of the moieties attached to the pyrrole ring.

Near-Field Spectral Response of Optically Excited Scanning Tunneling Microscope Junctions Probed by Single-Molecule Action Spectroscopy.

The near-field spectral response of metallic nanocavities is a key characteristic in plasmon-assisted photophysical and photochemical processes. Here, we show that the near-field spectral response of an optically excited plasmonic scanning tunneling microscope (STM) junction can be probed by single-molecule reactions that serve as a nanoscale sensor detecting the local field intensity. Near-field action spectroscopy for the cis ↔ cis tautomerization of porphycene on a Cu(110) surface reveals that the field enhancement in the STM junction largely depends on microscopic structures not only on the tip apex, but also on its shaft.

Unusual effects in single molecule tautomerization: hemiporphycene.

Parent hemiporphycene, a recently obtained constitutional isomer of porphyrin, exists in room temperature solutions and polymer matrices in the form of two trans tautomers interconverting via double hydrogen transfer. Using confocal fluorescence microscopy, it was possible to monitor tautomerization in single hemiporphycene molecules embedded in a PMMA film by monitoring the spectral and temporal evolution of their fluorescence spectra. The emission spectra of the two tautomeric forms are similar to those obtained from ensemble studies.

Plasmon-Mediated Surface Engineering of Silver Nanowires for Surface-Enhanced Raman Scattering.

We reveal nanoscale morphological changes on the surface of a silver nanowire (AgNW) in the conventional surface-enhanced Raman scattering (SERS) measurement condition. The surface morphology changes are due to the surface plasmon-mediated photochemical etching of silver in the presence of certain Raman probes, resulting in a dramatic increase of Raman scattering intensity. This observation indicates that the measured SERS enhancement does not always originate from the as-designed/fabricated structures themselves, but sometimes with contribution from the morphological changes by plasmon-mediated photochemical reactions.

Spectroscopic and microscopic investigations of tautomerization in porphycenes: condensed phases, supersonic jets, and single molecule studies.

We describe various experimental approaches that have been used to obtain a detailed understanding of double hydrogen transfer in porphycene, a model system for intramolecular hydrogen bonding and tautomerism. The emerging picture is that of a multidimensional tautomerization coordinate, with several vibrational modes acting as reaction-promoters or inhibitors through anharmonic intermode coupling. Tunnelling processes, coherent in the case of isolated molecules and incoherent in condensed phases, are found to play a major role even at elevated temperatures.