We show the real-space observation of fast and slow pulses propagating inside a photonic crystal waveguide by time-resolved near-field scanning optical microscopy. Local phase and group velocities of modes are measured. For a specific optical frequency we observe a localized pattern associated with a flat band in the dispersion diagram. During at least 3 ps, movement of this field is hardly discernible: its group velocity would be at most c=1000. The huge trapping times without the use of a cavity reveal new perspectives for dispersion and time control within photonic crystals.

The phase evolution of light in an optical waveguide structure has for the first time been visualized with subwavelength resolution using a novel heterodyne interferometric photon scanning tunneling microscope. Phase singularities in the optical field of the waveguide have been observed. The phase singularities of charge one appear at locations where the modal field amplitude vanishes, due to the interference of various modes in the waveguide. Excellent agreement of the data with calculations has been obtained.

We show that the propagation of a femtosecond laser pulse inside a photonic structure can be directly visualized and tracked as it propagates using a time-resolved photon scanning tunneling microscope. From the time-dependent and phase-sensitive measurements, both the group velocity and the phase velocity are unambiguously and simultaneously determined. It is expected that this technique will find applications in the investigation of the local dynamic behavior of photonic crystals and integrated optical circuits.

Heterogeneous optical behavior of perylene polyisocyanides, which arises from different structures of the polymer backbone, is revealed by the combination of single‐molecule fluorescence spectroscopy and atomic force microscopy. Short nonhelical perylene oligomers exhibit monomer‐like fluorescence properties, whereas long helical perylene fiber emission arises from excimer sites after delocalization of the excitation along the polymer backbone (see picture).

Directionality of electron transfer and long-lived charge separation are of key importance for efficient photocatalytic water splitting. Knowledge of the processes that follow photoexcitation is essential for the optimization of supramolecular assembly designs in order to improve the efficiency of photocatalytic hydrogen generation. Photoinduced intramolecular electron transfer processes within the hydrogen-evolving photocatalyst [Ru(bpy) 2 (tpy)Pd(CH 3 CN)Cl] 2+ (RuPd; bpy = bipyridine, tpy = 2,2′:5′,2″-terpyridine) have been studied by resonance Raman, femtosecond transient absorption, and time-resolved photoluminescence spectroscopies. Comparison of the photophysical properties of RuPd with those of the mononuclear precursor [(bpy) 2 Ru(tpy)] 2+ (Ru) enables establishment of a photophysical model ranging from the femtosecond to the submicrosecond domain. Optical excitation of Ru and RuPd populates both bpy-and tpy-based 1 MLCT (metal-to-ligand charge transfer) singlet states, from where intersystem crossing (ISC) into corresponding 3 MLCT triplet states occurs. Electron density localized on the peripheral bpy ligands can subsequently flow to the tpy bridging ligand by interligand electron transfer, which process occurs with a time constant of 32.5 (±1.5) ps for RuPd. Not all electron density undergoes this process, most likely due to a competing loss channel on the bpy ligand caused by vibrational relaxation occurring at a time scale of 9.1 (±0.4) ps. The relaxed 3 MLCT bpy and 3 MLCT tpy states have excited state lifetimes of 400 (±1) ns and 88 (±1) ns, respectively. Electron transfer from the tpy ligand to Pd may take place on a ∼100 ns time scale, but it is also possible that the final relaxed excited state is delocalized over the tpy ligand and the Pd center. The insight that optical excitation populates both the peripheral bpy ligands and the bridging tpy ligand, and that part of the electron density subsequently flows from the former to the latter, is important for the realization of efficient photocatalytic hydrogen generation. The next step is to make the interligand electron transfer process faster, by functionalizing the peripheral ligands with electron-donating moieties, and adapting the nature of the bridging ligand and the catalytic metal center.