Molecules can efficiently and selectively convert light energy into other degrees of freedom. Disentangling the underlying ultrafast motion of electrons and nuclei of the photoexcited molecule presents a challenge to current spectroscopic approaches. Here we explore the photoexcited dynamics of molecules by an interaction with an ultrafast X-ray pulse creating a highly localized core hole that decays via Auger emission. We discover that the Auger spectrum as a function of photoexcitation-X-ray-probe delay contains valuable information about the nuclear and electronic degrees of freedom from an element-specific point of view. For the nucleobase thymine, the oxygen Auger spectrum shifts towards high kinetic energies, resulting from a particular C-O bond stretch in the pp* photoexcited state. A subsequent shift of the Auger spectrum towards lower kinetic energies displays the electronic relaxation of the initial photoexcited state within 200 fs. Ab-initio simulations reinforce our interpretation and indicate an electronic decay to the np* state.

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Experimental evidence is presented for confinement resonances associated with photoabsorption by a Xe atom in a C60 cage. The giant 4d resonance in photoionization of Xe is predicted to be redistributed into four components due to multipath interference of photoelectron waves reflected by the cage. The measurements were made in the photon energy range 60-150 eV by merging a beam of synchrotron radiation with a mass/charge selected Xe@C₆₀+ ion beam. The phenomenon was observed in the Xe@C(58)(3+) product ion channel. [corrected]

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Mass-selected beams of atomic Ceq+ ions (q = 2, 3, 4), of C82+ and of endohedral Ce@C82+ ions were employed to study photoionization of free and encaged cerium atoms. The Ce 4d inner-shell contributions to single and double ionization of the endohedral Ce@C82+ fullerene have been extracted from the data and compared with expectations based on theory and the experiments with atomic Ce ions. Dramatic reduction and redistribution of the ionization contributions to 4d photoabsorption is observed. More than half of the Ce 4d oscillator strength appears to be diverted to the additional decay channels opened by the fullerene cage surrounding the Ce atom.

The main biological factors responsible for the variability of pollutant concentrations in cetaceans are reviewed. Diet is significant because many pollutants are concentrated through food webs. This explains most interspecific differences in pollutant levels and it may also contribute to variation among populations of the same species or even among different components of the same population when diet is subject to age-related or sex-related variations. The effect of body size is complex. Excretion rate and activity of detoxifying enzymes decrease as body weight increases, processes which would lead to higher pollutant concentrations in large animals. In contrast, a high metabolic rate, which is inversely correlated to body size, is associated with high pollutant concentrations. These opposing effects usually result in higher residue levels in smaller individuals. Body composition affects the contribution of each body compartment to the overall pollutant load. Therefore, the body load of lipophilic pollutants will strongly depend on the relative mass of blubber, a variable that shows a threefold variation among cetacean species or, in seasonal feeders, among individuals. Nutritive condition also affects the dynamics of lipophilic pollutants. Lipid mobilisation results in an increase in residue levels, but this variation is not as large as a purely concentrative model would suggest because of enhancement of detoxification processes following a rise in tissue pollutant concentrations. Disease affects pollutant levels in different ways: impoverishing nutritive condition; altering normal physiological functions; and depressing reproduction therefore reducing reproductive transfer in females. The combined result of these processes is usually an increase in pollutant levels in diseased individuals. The concentration of lipophilic pollutants normally increases with age in males because input exceeds the ability of the organism to excrete pollutants. Variable proportions of the pollutant load are transferred to offspring during gestation and lactation, for which reason tissue concentrations in females decrease or stabilise, thus producing lower residue levels than in males. However, because not all compounds are transferred at the same rate, their relative abundance varies with age and sex.Intensity of reproductive transfer is also associated with the reproductive traits of the species, particularly the length of lactation. With the exception of zinc, concentrations of heavy metals increase with age in both sexes but, by contrast with lipophilic pollutants, concentrations in females are similar or higher than in males. The significance of these factors of variation should be taken into account when designing sampling methodology, comparing sample groups, or evaluating toxicological impact.

This Letter was published online on 15 November 2010 with a tagging error in the abstract. The last sentence of the abstract should read as ''The phenomenon was observed in the Xe@C 3þ 58 product ion channel.'' The

We have investigated L-shell photoionization (PI) of 1S ground-state and 3Po metastable states of the Be-like ion, B+, in the photon energy range 22.4–31.3 eV, at an experimental energy resolution of 25 meV. Absolute PI cross sections have been measured using a photon–ion merged-beams arrangement at the Advanced Light Source. Detailed calculations using the semi-relativistic Breit–Pauli R-matrix approach suggest a fraction of 29% of metastable ions in the primary beam of the experiment. Excellent agreement is observed between the theoretical predictions and the experimental high-resolution PI cross sections. The present results are compared with earlier experimental and theoretical work. The cross section for PI of B+ ground-state ions can be very well described by an analytic formula derived from quantum defect theory.