Improving the Quantum Yields of Perylene Diimide Aggregates by Increasing Molecular Hydrophobicity in Polar Media.

Here we report the quantum yield of four aggregated perylene diimide (PDI) species that vary by the length of the branched side chains attached at the N,N' imide positions. The PDI molecules were dissolved in binary water:methanol solvents as a means to vary the solvent polarity and control the degree of aggregation in solution. By performing spectroscopy, kinetics, and light scattering experiments, the nature of the molecular interactions in the solutions was determined. The maximum quantum yield of the aggregated molecules increased from 0.04 for the shortest chain molecule (B2) to 0.20 for the largest chain molecule (B13). The higher quantum yield of B13 compared with B2 correlates well with an increase in the fluorescence lifetime. The monomer emission lifetime was 4.8 ns whereas a lifetime as high as 21.2 ns was measured for the B13 aggregate fluorescence. A shorter sub-nanosecond lifetime was also measured for suspended colloids in B5, B9, and B13. The enhanced quantum yield is attributed to an increase of disorder in the B13 aggregates. As the polarity of the solution increases, the hydrophobic effect further enhances the disorder, and, therefore, the quantum yields in these particles.

Role of the polymer matrix on the photoluminescence of embedded CdSe quantum dots.

The photoluminescence (PL) of CdSe quantum dots (QDs) that form stable nanocomposites with polymer liquid crystals (LCs) as smectic C hydrogen-bonded homopolymers from a family of poly[4-(n-acryloyloxyalkyloxy)benzoic acids] is reported. The matrix that results from the combination of these units with methoxyphenyl benzoate and cholesterol-containing units has a cholesteric structure. The exciton PL band of QDs in the smectic matrix is redshifted with respect to QDs in solution, whereas a blueshift is observed with the cholesteric matrix. The PL lifetimes and quantum yield in cholesteric nanocomposites are higher than those in smectic ones. This is interpreted in terms of a higher order of the smectic matrix in comparison to the cholesteric one. CdSe QDs in the ordered smectic matrix demonstrate a splitting of the exciton PL band and an enhancement of the photoinduced differential transmission. These results reveal the effects of the structure of polymer LC matrices on the optical properties of embedded QDs, which offer new possibilities for photonic applications of QD-LC polymer nanocomposites.

Control of coherent excitation of neon in the extreme ultraviolet regime.

Coherent excitation of a superposition of Rydberg states in neon by the 13th harmonic of an intense 804 nm pulse and the formation of a wave packet is reported. Pump-probe experiments are performed, where the 3d-manifold of the 2p6-->2p5 (2P3/2) 3d [1/2]1- and 2p6-->2p5 (2P3/2) 3d [3/2]1-transitions are excited by an extreme ultraviolet (XUV) radiation pulse, which is centered at 20.05 eV photon energy. The temporal evolution of the excited state population is probed by ionization with a time-delayed 804 nm pulse. Control of coherent transient excitation and wave packet dynamics in the XUV-regime is demonstrated, where the spectral phase of the 13th harmonic is used as a control parameter. Modulation of the phase is achieved by propagation of the XUV-pulse through neon of variable gas density. The experimental results indicate that phase-shaped high-order harmonics can be used to control fundamental coherent excitation processes in the XUV-regime.

Two-color visible/vacuum ultraviolet photoelectron imaging dynamics of Br2.

An experimental two-color photoionization dynamics study of laser-excited Br2 molecules is presented, combining pulsed visible laser excitation and tunable vacuum ultraviolet (VUV) synchrotron radiation with photoelectron imaging. The X 1Sigmag + -B 3Pi0+u transition in Br2 is excited at 527 nm corresponding predominantly to excitation of the v' = 28 vibrational level in the B 3Pi0+u state. Tunable VUV undulator radiation in the energy range of 8.40-10.15 eV is subsequently used to ionize the excited molecules to the X 2Pi32,12 state of the ion, and the ionic ground state is probed by photoelectron imaging. Similar experiments are performed using single-photon synchrotron ionization in the photon energy range of 10.75-12.50 eV without any laser excitation. Photoelectron kinetic energy distributions are extracted from the photoelectron images. In the case of two-color photoionization using resonant excitation of the intermediate B 3Pi0+u state, a broad distribution of photoelectron kinetic energies is observed, and in some cases even a bimodal distribution, which depends on the VUV photon energy. In contrast, for single-photon ionization, a single nearly Gaussian-shaped distribution is observed, which shifts to higher energy with photon energy. Simulated spectra based on Franck-Condon factors for the transitions Br2(X 1Sigmag+, v" = 0)-Br2 +(X 2Pi12,32, v+) and Br2(B 3Pi0+u, v' = 28)-Br2 +(X 2Pi12,32, v+) are generated. Comparison of these calculated spectra with the measured images suggests that the differences in the kinetic energy distributions for the two ionization processes reflect the different extensions of the vibrational wave functions in the v" = 0 electronic ground state (X 1Sigmag+) versus the electronically and vibrationally excited state (B 3Pi0+u, v' = 28).