Ultrafast spectroscopy of single molecules

We present a single-molecule study on femtosecond dynamics in multichromophoric systems, combining fs pump-probe, emission-spectra and fluorescence-lifetime analysis. At the single molecule level a wide range of exciton delocalisation lengths and energy redistribution times is revealed. Next, two color pump-probe experiments are presented as a step to addressing ultrafast energy transfer in individual complexes

Phase mapping of ultrashort pulses in bimodal photonic structures: A window on local group velocity dispersion

The amplitude and phase evolution of ultrashort pulses in a bimodal waveguide structure has been studied with a time-resolved photon scanning tunneling microscope (PSTM). When waveguide modes overlap in time intriguing phase patterns are observed. Phase singularities, arising from interference between different modes, are normally expected at equidistant intervals determined by the difference in effective index for the two modes. However, in the pulsed experiments the distance between individual singularities is found to change not only within one measurement frame, but even depends strongly on the reference time. To understand this observation it is necessary to take into account that the actual pulses generating the interference signal change shape upon propagation through a dispersive medium. This implies that the spatial distribution of phase singularities contains direct information on local dispersion characteristics. At the same time also the mode profiles, wave vectors, pulse lengths, and group velocities of all excited modes in the waveguide are directly measured. The combination of these parameters with an analytical model for the time-resolved PSTM measurements shows that the unique spatial phase information indeed gives a direct measure for the group velocity dispersion of individual modes. As a result interesting and useful effects, such as pulse compression, pulse spreading, and pulse reshaping become accessible in a local measuremen

Energy transfer in single molecular photonic wires

Molecular photonics is a new emerging field of research around the premise that it is possible to develop optical devices using single molecules as building blocks. Truly technological impact in the field requires focussed efforts on designing functional molecular devices as well as having access to their photonic properties on an individual basis. In this Minireview we discuss our approach towards the design and single-molecule investigation of one-dimensional multimolecular arrays intended to work as molecular photonic wires. Three different schemes have been explored: a) perylene-based dimer and trimer arrays displaying coherent exciton delocalisation at room temperature; b) DNA-based unidirectional molecular wires containing up to five different chromophores and exhibiting weak excitonic interactions between neighbouring dyes; and c) one-dimensional multichromophoric polymers based on perylene polyisocyanides showing excimerlike emission. As a whole, our single-molecule data show the importance of well-defined close packing of chromophores for obtaining optimal excitonic behaviour at room temperature. Further improvement on (bio)chemical synthesis, together with the use of single-molecule techniques, should lead in the near future to efficient and reliable photonic wires with true device functionality

Single-molecule photobleaching probes the exciton wave function in a multichromophoric system

Ajuts: This work has been supported by the EC Program IHP- 99 (HPMF-CT-2002-01698)The exciton wave function of a trichromophoric system is investigated by means of single molecule spectroscopy at room temperature. Individual trimers exhibit superradiance and loss of vibronic structure in emission spectrum, features proving exciton delocalization. We identify two distinct photodegradation pathways for single trimers upon sequential photobleaching of the chromophores. The rate of each pathway is a measure for the contribution of the separate dyes to the collective excited state of the system, in this way probing the wave function of the delocalized exciton