Optical and morphological properties of thin films of bis-pyrenyl π-conjugated molecules.

1,4-Di-n-octyloxy-2,5-bis(pyren-1-ylethenyl)benzene (bis-pyrene) has been studied by the means of surface cavity ring-down (s-CRD) spectroscopy on an amorphous BK7 glass substrate and scanning tunnelling microscopy (STM) on Au(111). Absorption spectra show a modification of the optical properties as a function of coverage, i.e. appearance of a shoulder around 505 nm followed by a saturation of the intensity of this signal observed at higher coverages. We attribute this shoulder to the change of the molecular orientation between the first and the second monolayer and thus to an interfacial effect. These results are confirmed by scanning tunnelling microscopy (STM) measurements where the bis-pyrene molecules have been deposited on Au(111) at room temperature (RT) and onto a cold substrate. Independently of the temperature in the range from 210 K to RT, the first monolayer is always highly organized. At low temperature bis-pyrene molecules constituting the second monolayer are randomly distributed, suggesting that self-organisation is kinetically hindered. Deposited at room temperature, the molecular diffusion is enhanced and the formation of an organized second layer takes place after storing the sample for 150 minutes at room temperature. A HOMO-LUMO gap of 2.85 eV has been determined by scanning tunnelling spectroscopy, which is in very good agreement with the observed optical transition at 434 nm (2.86 eV) in s-CRD spectroscopy.

Plasmons in supported size-selected silver nanoclusters.

The plasmonic behavior of size-selected supported silver clusters is studied by surface second harmonic generation spectroscopy for the first time. A blue shift of ∼0.2 eV in the plasmon resonance is observed with decreasing cluster size from Ag55 to Ag9. In addition to the general blue shift, a nonscalable size-dependence is also observed in plasmonic behavior of Ag nanoclusters, which is attributed to varying structural properties of the clusters. The results are in quantitative agreement with a hybrid theoretical model based on Mie theory and the existing DFT calculations.

Orientational changes of supported chiral 2,2'-dihydroxy-1,1'binaphthyl molecules.

Well defined thin molecular films of 2,2'-dihydroxy-1,1'binaphthyl (binol) molecules at coverages between 5 × 10(15) molecules per cm(2) and 10(17) molecules per cm(2) on thin glass (BK7) substrates were investigated under ultra-high-vacuum (UHV) conditions. Second-Harmonic-Generation Optical-Rotatory-Dispersion measurements (SHG-ORD) were performed using a dedicated spectroscopic setup which allows for the determination of the rotation angle of the SH-signal of two enantiomers. Rotation angles of up to 38 degrees were measured. The chirality of the two enantiomers has been studied at 674 nm (337 nm resonance wavelength) in the transmission mode. Coverage dependent orientation evolution of binol molecular films was revealed by precise monitoring of the surface coverage while performing SHG-ORD experiments. We show that the molecules reach their final orientation at a surface coverage of 5 × 10(16) molecules per cm(2). From the obtained experimental data the ratio of chiral and achiral susceptibility components could be calculated and was observed to change with coverage.