Photochemical Control of Exciton Superradiance in Light-Harvesting Nanotubes.

Photosynthetic antennae and organic electronic materials use topological, structural, and molecular control of delocalized excitons to enhance and direct energy transfer. Interactions between the transition dipoles of individual chromophore units allow for coherent delocalization across multiple molecular sites. This delocalization, for specific geometries, greatly enhances the transition dipole moment of the lowest energy excitonic state relative to the chromophore and increases its radiative rate, a phenomenon known as superradiance. In this study, we show that ordered, self-assembled light-harvesting nanotubes (LHNs) display excitation-induced photobrightening and photodarkening. These changes in quantum yield arise due to changes in energetic disorder, which in turn increases/decreases excitonic superradiance. Through a combination of experiment and modeling, we show that intense illumination induces different types of chemical change in LHNs that reproducibly alter absorption and fluorescence properties, indicating control over excitonic delocalization. We also show that changes in spectral width and shift can be sensitive measures of system dimensionality, illustrating the mixed 1-2D nature of LHN excitons. Our results demonstrate a path forward for mastery of energetic disorder in an excitonic antenna, with implications for fundamental studies of coherent energy transport.

Robust excitons inhabit soft supramolecular nanotubes.

Nature's highly efficient light-harvesting antennae, such as those found in green sulfur bacteria, consist of supramolecular building blocks that self-assemble into a hierarchy of close-packed structures. In an effort to mimic the fundamental processes that govern nature's efficient systems, it is important to elucidate the role of each level of hierarchy: from molecule, to supramolecular building block, to close-packed building blocks. Here, we study the impact of hierarchical structure. We present a model system that mirrors nature's complexity: cylinders self-assembled from cyanine-dye molecules. Our work reveals that even though close-packing may alter the cylinders' soft mesoscopic structure, robust delocalized excitons are retained: Internal order and strong excitation-transfer interactions--prerequisites for efficient energy transport--are both maintained. Our results suggest that the cylindrical geometry strongly favors robust excitons; it presents a rational design that is potentially key to nature's high efficiency, allowing construction of efficient light-harvesting devices even from soft, supramolecular materials.

Coherent exciton dynamics in supramolecular light-harvesting nanotubes revealed by ultrafast quantum process tomography.

Long-lived exciton coherences have been recently observed in photosynthetic complexes via ultrafast spectroscopy, opening exciting possibilities for the study and design of coherent exciton transport. Yet, ambiguity in the spectroscopic signals has led to arguments against interpreting them in terms of exciton dynamics, demanding more stringent tests. We propose a novel strategy, quantum process tomography (QPT), for ultrafast spectroscopy and apply it to reconstruct the evolving quantum state of excitons in double-walled supramolecular light-harvesting nanotubes at room temperature from eight narrowband transient grating experiments. Our analysis reveals the absence of nonsecular processes, unidirectional energy transfer from the outer to the inner wall exciton states, and coherence between those states lasting about 150 fs, indicating weak electronic coupling between the walls. Our work constitutes the first experimental QPT in a "warm" and complex system and provides an elegant scheme to maximize information from ultrafast spectroscopy experiments.

Chemi-luminescence measurements of hyperthermal Xe+/Xe2+ + NH3 reactions.

Luminescence spectra are recorded for the reactions of Xe(+) + NH(3) and Xe(2+) + NH(3) at energies ranging from 11.5 to 206 eV in the center-of-mass (E(cm)) frame. Intense features of the luminescence spectra are attributed to the NH (A (3)Π(i)-X (3)Σ(-)), hydrogen Balmer series, and Xe I emission observable for both primary ions. Evidence for charge transfer products is only found through Xe I emission for both primary ions and NH(+) emission for Xe(2+) primary ions. For both primary ions, the absolute NH (A-X) cross section increases with collision energy before leveling off at a constant value, approximately 9 × 10(-18) cm(2), at about 50 eV while H-α emission increases linearly with collision energy. The nascent NH (A) populations derived from the spectral analysis are found to be independent of collision energy and have a constant rotational temperature of 4200 K.

Tunable frequency-controlled isolated attosecond pulses characterized by either 750 nm or 400 nm wavelength streak fields.

A compact and robust Mach-Zehnder type interferometer coupled with the double optical gating technique provides tunable isolated attosecond pulses and streak field detection with fields centered at either 750 nm or 400 nm. Isolated attosecond pulses produced at 45 eV (with measured pulse duration of 114 ± 4 as) and 20 eV (with measured pulse duration of 395 ± 6 as) are temporally characterized with a 750 nm wavelength streak field. In addition, an isolated 118 ± 10 as pulse at 45 eV is measured with a 400 nm wavelength streak field. The interferometer design used herein provides broad flexibility for attosecond streak experiments, allowing pump and probe pulses to be specified independently. This capability is important for studying selected electronic transitions in atoms and molecules.