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Doubly-excited atoms are known to autoionize. It is shown that in the presence of a neighboring atom, there is competition between autoionization and ICD (Interatomic Coulombic Decay) where the doubly-excited atom partially relaxes and the neighbor ionizes. Through a Rydberg series of doubly-excited states, the autoionization rate decreases in contrast to the ICD rate and ICD becomes dominant. Depending on the nature of the neighbor and the number of neighbors, other interatomic processes become operative even after autoionization, all demonstrating that the physics of doubly-excited species is strongly enriched in the presence of neighbors. Explicit examples are discussed.

The X-ray absorption spectra (XAS) of Ar-2 and ArNe dimers and small Ar clusters in the L-2,L-3 region (244-252 eV) of the Ar atom have been recorded using synchrotron light and a combination of coincidence methods and kinetic energy discrimination of energetic ions. The absorption peaks in the spectra of the dimers and clusters were found to be shifted and broadened relative to the peaks in the spectrum of the Ar atom. In order to unambiguously relate these chemical shifts to the electronic structure of the core excited states in dimers, we performed ab initio calculations of the XAS spectra. Implications of the results for the use of XAS as a structure determination method in large rare gas clusters are discussed.

The hitherto unexplored two-photon doubly excited states [Ne∗(2p-13s)]2 were experimentally identified using the seeded, fully coherent, intense extreme ultraviolet free-electron laser FERMI. These states undergo ultrafast interatomic Coulombic decay (ICD), which predominantly produces singly ionized dimers. In order to obtain the rate of ICD, the resulting yield of Ne2+ ions was recorded as a function of delay between the extreme ultraviolet pump and UV probe laser pulses. The extracted lifetimes of the long-lived doubly excited states, 390(-130/+450) fs, and of the short-lived ones, less than 150 fs, are in good agreement with ab initio quantum mechanical calculations.

The hitherto unexplored two-photon doubly excited states [Ne^{*}(2p^{-1}3s)]_{2} were experimentally identified using the seeded, fully coherent, intense extreme ultraviolet free-electron laser FERMI. These states undergo ultrafast interatomic Coulombic decay (ICD), which predominantly produces singly ionized dimers. In order to obtain the rate of ICD, the resulting yield of Ne_{2}^{+} ions was recorded as a function of delay between the extreme ultraviolet pump and UV probe laser pulses. The extracted lifetimes of the long-lived doubly excited states, 390(-130/+450) fs, and of the short-lived ones, less than 150 fs, are in good agreement with ab initio quantum mechanical calculations.

The impact of the solvent on the photodissociation of embedded molecules has been intensively investigated in the last decades. Collisions of photofragments with the solvating atoms or molecules can change their kinetic energy distribution or even lead to the de-excitation of the dissociating molecule to a bound electronic state quenching the dissociation. In this article we show that this cage effect is strongly enhanced if interatomic Coulombic decay (ICD) of the excited state becomes allowed. Ab initio calculations in H2O-Cl(-) cluster show that the ultra-fast dissociation of water in the à excited state is strongly quenched by ICD. We found that this very efficient quenching is due to two factors. First, the lifetimes of the à state due to ICD are short ranging between 6 and 30 fs. Second, nuclear dynamics is dominated by the chattering motion of the H atom between O and Cl(-) allowing ICD to act for longer times. We hope that this work will be an important first step in clarifying the impact of ICD on photodissociation of embedded molecules.

Natural selection has directed the evolution of floral traits so that pollinator visits are manipulated to maximize the fitness of individual plants by directing which other individual sires its seeds. In some plants, flowers change color over time and may have the ability to direct pollinators to rewarding flowers. In addition, by varying when pollen is available and when stigmas are receptive, protandrous plants can show variation in selfing rates. In this study, the association between color change and gender transition in flowers of Saponaria officinalis was examined. Anthocyanins were extracted from flowers of each gender stage to measure color using spectrophotometry. Female-phase flowers were found to have significantly higher anthocyanin concentration than male-phase flowers in both natural populations and experimental plots. This color change corresponded to a decrease in male sexual function, which was measured by the percentage of pollen grains stained as viable by lactophenol aniline blue and germinated on Brewbaker–Kwack media. Color change was phenotypically plastic. Plants grown in full sun had a more extensive color change than those grown in shaded experimental plots, and this effect was reversed the following year when the shading was removed. Pollinator observations documented both diurnal and nocturnal insect visitation. Fruit and seed set were equivalent on inflorescences bagged during daylight versus night, indicating that both diurnal and nocturnal insects are effective pollinators. If pollinators discriminate based on color, this could potentially reduce within-plant floral visits and also geitonogamy. This study is the first to document flower color change and moth pollination in Saponaria officinalis.

When an excited atom is embedded into an environment, novel relaxation pathways can emerge that are absent for isolated atoms. A well-known example is interatomic Coulombic decay, where an excited atom relaxes by transferring its excess energy to another atom in the environment, leading to its ionization. Such processes have been observed in clusters ionized by extreme-ultraviolet and X-ray lasers. Here, we report on a correlated electronic decay process that occurs following nanoplasma formation and Rydberg atom generation in the ionization of clusters by intense, non-resonant infrared laser fields. Relaxation of the Rydberg states and transfer of the available electronic energy to adjacent electrons in Rydberg states or quasifree electrons in the expanding nanoplasma leaves a distinct signature in the electron kinetic energy spectrum. These so far unobserved electron-correlation-driven energy transfer processes may play a significant role in the response of any nano-scale system to intense laser light., In clusters, relaxation of excited atoms can lead to ionization of nearby atoms, a process known as interatomic Coulomb decay. Here, the authors report on a so far unobserved correlated electronic decay process following Rydberg atom generation in clusters ionized by intense near-infrared fields.

We report on a novel correlated electronic decay process following extensive Rydberg atom formation in clusters ionized by intense near-infrared fields. A peak close to the atomic ionization potential is found in the electron kinetic energy spectrum. This new contribution is attributed to an energy transfer between two electrons, where one electron decays from a Rydberg state to the ground state and transfers its excess energy to a weakly bound cluster electron in the environment that can escape from the cluster. The process is a result of nanoplasma formation and is therefore expected to be important, whenever intense laser pulses interact with nanometer-sized particles.

We report on the observation of a novel intracluster Coulombic decay process following Rydberg atom formation in clusters ionized by intense near-infrared fields. A new decay channel emerges, in which a Rydberg atom relaxes to the ground state by transferring its excess energy to a weakly bound electron in the environment that is emitted from the cluster. We find evidence for this process in the electron spectra, where a peak close to the corresponding atomic ionization potential is observed. For Ar clusters, a decay time of 87 ps is measured, which is significantly longer than in previous time-resolved studies of interatomic Coulombic decay.

Excitation of two identical species in a cluster by the absorption of two photons of the same energy is strongly suppressed since the excitation of one subunit blocks the excitation of the other one due to the binding Coulomb interaction. Here, we propose a very efficient way to overcome this blockade in producing doubly-excited homoatomic clusters by a single intense laser pulse. For Ne$_2$ it is explicitly demonstrated that the optimal carrier frequency of the pulse is given by half of the energy of the target state, which allows one to doubly excite more than half of the dimers at moderate field intensities. These dimers then undergo ultrafast interatomic decay bringing one Ne to its ground state and ionizing the other one. The reported \emph{ab initio} electron spectra present reliable predictions for future experiments by strong laser pulses., Comment: 5 figs

Ne clusters (∼5000 atoms) were resonantly excited (2p→3s) by intense free electron laser (FEL) radiation at FERMI. Such multiply excited clusters can decay nonradiatively via energy exchange between at least two neighboring excited atoms. Benefiting from the precise tunability and narrow bandwidth of seeded FEL radiation, specific sites of the Ne clusters were probed. We found that the relaxation of cluster surface atoms proceeds via a sequence of interatomic or intermolecular Coulombic decay (ICD) processes while ICD of bulk atoms is additionally affected by the surrounding excited medium via inelastic electron scattering. For both cases, cluster excitations relax to atomic states prior to ICD, showing that this kind of ICD is rather slow (picosecond range). Controlling the average number of excitations per cluster via the FEL intensity allows a coarse tuning of the ICD rate.