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At the beginning of 2011, the former Forschungszentrum Dresden-Rossendorf (FZD) was fully integrated into the Helmholtz Association, as Helmholtz-Zentrum Dresden-Rossendorf (HZDR). Therefore, the present Annual Report 2010 of the Institute of Radiochemistry (IRC) is published as the first HZDR-Report. The Institute of Radiochemistry is one of the six Research Institutes of this centre. IRC contributes to the research program “Nuclear Safety Research” in the “Research Field of Energy” and performs basic and applied research in radiochemistry and radioecology. Motivation and background of our research are environmental processes relevant for the installation of nuclear waste repositories, for remediation of uranium mining and milling sites, and for radioactive contaminations caused by nuclear accidents and fallout. Because of their high radiotoxicity and long half-life the actinides are of special interest.

We report infrared photodissociation (IRPD) spectra for the D2-tagged titanium oxide cluster anions (TiO2)−n with n = 3–8 in the spectral region from 450 to 1200 cm−1. The IRPD spectra are interpreted with the aid of harmonic spectra from BP86/6-311+G* density functional theory calculations of energetically low-lying isomers. We conclusively assign the IRPD spectra of the n = 3 and n = 6 clusters to global minimum energy structures with Cs and C2 symmetry, respectively. The vibrational spectra of the n = 4 and n = 7 clusters can be attributed to contributions of at most two low-lying structures. While our calculations indicate that the n = 5 and n = 8 clusters have many more low-lying isomers than the other clusters, the dominant contributions to their spectra can be assigned to the lowest energy structures. Through comparison between the calculated and experimental spectra, we can draw conclusions about the size-dependent evolution of the properties of (TiO2)−n clusters, and on their potential utility as model systems for catalysis on a bulk TiO2 surface.

We use cryogenic ion trap vibrational spectroscopy in combination with quantum chemical calculations to study the structure of mono- and dialuminum oxide anions. The infrared photodissociation spectra of D2-tagged AlO1-4 − and Al2O3-6 − are measured in the region from 400 to 1200 cm−1. Structures are assigned based on a comparison to simulated harmonic and anharmonic IR spectra derived from electronic structure calculations. The monoaluminum anions contain an even number of electrons and exhibit an electronic closed-shell ground state. The Al2O3-6 − anions are oxygen-centered radicals. As a result of a delicate balance between localization and delocalization of the unpaired electron, only the BHLYP functional is able to qualitatively describe the observed IR spectra of all species with the exception of AlO3 −. Terminal Al–O stretching modes are found between 1140 and 960 cm−1. Superoxo and peroxo stretching modes are found at higher (1120-1010 cm−1) and lower energies (850-570 cm−1), respectively. Four modes in-between 910 and 530 cm−1 represent the IR fingerprint of the common structural motif of dialuminum oxide anions, an asymmetric four-member Al–(O)2–Al ring.

Infrared photodissociation is used to record the vibrational spectrum of FeO2+(He)2–4 which shows three bands at 1035, 980, and 506 cm−1. Quantum chemical multi-reference configuration interaction calculations (MRCISD) of structures and harmonic frequencies show that these bands are due to two different isomers, an inserted dioxo complex with Fe in the +V oxidation state and a side-on superoxo complex with Fe in the +II oxidation state. These two are separated by a substantial barrier, 53 kJ/mol, whereas the third isomer, an end-on complex between Fe+ and an O2 molecule, is easily converted into the side-on complex. For all three isomers, states of different spin multiplicity have been considered. Our best energies are computed at the MRCISD+Q level, including corrections for complete active space and basis set extension, core-valence correlation, relativistic effects, and zero-point vibrational energy. The average coupled pair functional (ACPF) yields very similar energies. Density functional theory (DFT) differs significantly from our best estimates for this system, with the TPSS functional yielding the best results. The other functionals tested are BP86, PBE, B3LYP, TPSSh, and B2PLYP. Complete active space second order perturbation theory, (CASPT2) performs better than DFT, but less good than ACPF.

Fourier Transform Infrared Spectroscopy and Broadband Dielectric Spectroscopy are combined to trace kinetics of mutarotation in L-fucose. After quenching molten samples down to temperatures between T=313 K and 328 K, the concentrations of two anomeric species change according to a simple exponential time dependence, as seen by an increase in absorbance of specific IR-vibrations. In contrast, the dielectric spectra reveal a slowing down of the structural (α-) relaxation process according to a stretched exponential time dependence (stretching exponent of 1.5 ± 0.2). The rates of change in the IR absorption for α- and β-fucopyranose are (at T = 313 K) nearly one decade faster than that of the intermolecular interactions as measured by the shift of the α-relaxation. This reflects the fact that the α-relaxation monitors the equilibration at a mesoscopic length scale, resulting from fluctuations in the anomeric composition.

Glassy dynamics of polymethylphenylsiloxane (PMPS) is studied by broadband dielectric spectroscopy in one-dimensional (1D) and two-dimensional (2D) nanometric confinement; the former is realized in thin polymer layers having thicknesses down to 5 nm, and the latter in unidirectional (thickness 50 µm) nanopores with diameters varying between 4 and 8 nm. Based on the dielectric measurements carried out in a broad spectral range at widely varying temperatures, glassy dynamics is analyzed in detail in 1D and in 2D confinements with the following results: (i) the segmental dynamics (dynamic glass transition) of PMPS in 1D confinement down to thicknesses of 5 nm is identical to the bulk in the mean relaxation rate and the width of the relaxation time distribution function; (ii) additionally a well separated surface induced relaxation is observed, being assigned to adsorption and desorption processes of polymer segments with the solid interface; (iii) in 2D confinement with native inner pore walls, the segmental dynamics shows a confinement effect, i.e., the smaller the pores are, the faster the segmental dynamics; on silanization, this dependence on the pore diameter vanishes, but the mean relaxation rate is still faster than in 1D confinement; (iv) in a 2D confinement, a pronounced surface induced relaxation process is found, the strength of which increases with the decreasing pore diameter; it can be fully removed by silanization of the inner pore walls; (v) the surface induced relaxation depends on its spectral position only negligibly on the pore diameter; (vi) comparing 1D and 2D confinements, the segmental dynamics in the latter is by about two orders of magnitude faster. All these findings can be comprehended by considering the density of the polymer; in 1D it is assumed to be the same as in the bulk, hence the dynamic glass transition is not altered; in 2D it is reduced due to a frustration of packaging resulting in a higher free volume, as proven by ortho-positronium annihilation lifetime spectroscopy.

Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphonium IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range—indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs.

Fluorescence intermittency is a random switching between emitting (on) and non-emitting (off) periods found for many single chromophores such as semiconductor quantum dots and organic molecules. The statistics of the duration of on- and off-periods are commonly determined by thresholding the emission time trace of a single chromophore and appear to be power law distributed. Here we test with the help of simulations if the experimentally determined power law distributions can actually reflect the underlying statistics. We find that with the experimentally limited time resolution real power law statistics with exponents αon/off ≳ 1.6, especially if αon ≠ αoff would not be observed as such in the experimental data after binning and thresholding. Instead, a power law appearance could simply be obtained from the continuous distribution of intermediate intensity levels. This challenges much of the obtained data and the models describing the so-called power law blinking.

The vibrational dynamics of theOH stretching mode in Ba(ClO4)2 trihydrate are investigated by means of femtosecond infrared spectroscopy. The sample offers plane cyclic water trimers in the solid phase that feature virtually no hydrogen bond interaction between thewater molecules. Selective excitation of the symmetric and asymmetric stretching leads to fast population redistribution, while simultaneous excitation yields quantum beats, which are monitored via a combination tone that dominates the overtone spectrum. The combination of steady-state and time-resolved spectroscopy with quantum chemical simulations and general theoretical considerations gives indication of various aspects of symmetry breakage. The system shows a joint population lifetime of 8 ps and a long-lived coherence between symmetric and asymmetric stretching, which decays with a time constant of 0.6 ps.