A detailed analysis of experimentally obtained temperature-dependent gas-phase kinetic data for the oxygen and carbon monoxide adsorption on small anionic gold (Au(n)(-), n = 1-3), silver (Ag(n)(-), n = 1-5), and binary silver-gold (Ag(n)Au(m)(-), n + m = 2, 3) clusters is presented. The Lindemann energy transfer model in conjunction with statistical unimolecular reaction rate theory is employed to determine the bond dissociation energies E(0) of the observed metal cluster complexes with O(2) and CO. The accuracy limits of the obtained binding energies are evaluated by applying different transition-state models. The assumptions involved in the data evaluation procedure as well as possible sources of error are discussed. The thus-derived binding energies of O(2) to pure silver and binary silver-gold cluster anions are generally in excellent agreement with previously reported theoretical values. In marked contrast, the binding energies of O(2) and CO to Au(2)(-) and Au(3)(-) determined via temperature-dependent reaction kinetics are consistently lower than the theoretically predicted values.

The ultrafast injection dynamics, early recombination dynamics, and spectral signatures of four systematically varied dye-metal oxide hybrid systems were investigated using transient absorption spectroscopy techniques. First, photoinduced electron transfer from two different perylene derivatives into zinc oxide (ZnO) colloidal films is reported. Here, the electronic coupling of the perylene chromophore 2,5-Di-tert-butyl-perylene-9-yl-propionic acid (1) to the ZnO colloids was weaker than the electronic coupling of the chromophore 2,5-Di-tert-butyl-perylene-9-yl-acrylic acid (2). Second, the photoinduced electron transfer of the same two molecules attached to TiO2 colloids was measured and compared to the results for the ZnO colloids using the same techniques. The temporal traces at both the excited-state and the cationic state of the chromophores attached to the semiconductor surfaces were measured simultaneously and showed very good agreement, which indicated a direct injection into the semiconductor. The overall injection times for the ZnO samples was as short as 190 fs, which suggested a strong electronic coupling element for these systems. This injection time is short compared to reports on similar ZnO hybrid systems, but it is still longer than the injection times reported for the TiO2 hybrid systems. The transient absorption spectra of molecule 2 attached to TiO2 showed a large negative signal at 530–550 nm, which indicated the presence of a direct charge transfer state contribution in this system.

The predictable quantum efficient detector (PQED) is intended to become a new primary standard for radiant power measurements in the wavelength range from 400 nm to 800 nm. Characterization results of custom-made single induced junction photodiodes as they are used in the PQED and of assembled PQEDs are presented. The single photodiodes were tested in terms of linearity and spatial uniformity of the spectral responsivity. The highly uniform photodiodes were proved to be linear over seven orders of magnitude, i.e. in the radiant power range from 100 pW to 400 µW. The assembled PQED has been compared with a cryogenic electrical substitution radiometer with a very low uncertainty of the order of 30 ppm. Experimental results show good agreement with the modelled response of the PQED to optical radiation and prove a near unity external quantum efficiency.

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