In this paper, we investigate HNCO by resonant and nonresonant Auger electron spectroscopy at the K-edges of carbon, nitrogen, and oxygen, employing soft X-ray synchrotron radiation. In comparison with the isosteric but linear CO molecule, spectra of the bent HNCO molecule are similar but more complex due to its reduced symmetry, wherein the degeneracy of the π-orbitals is lifted. Resonant Auger electron spectra are presented at different photon energies over the first core-excited 1s → 10a' resonance. All Auger electron spectra are assigned based on ab initio configuration interaction computations combined with the one-center approximation for Auger intensities and moment theory to consider vibrational motion. The calculated spectra were scaled by a newly introduced energy scaling factor, and generally, good agreement is found between experiment and theory for normal as well as resonant Auger electron spectra. A comparison of resonant Auger spectra with nonresonant Auger structures shows a slight broadening as well as a shift of the former spectra between -8 and -9 eV due to the spectating electron. Since HNCO is a small molecule and contains the four most abundant atoms of organic molecules, the reported Auger electron decay spectra will provide a benchmark for further theoretical approaches in the computation of core electron spectra.

Photoexcitation of a newly synthesized, neutral tetrasubstituted Ge9cluster with a covalently bound transition metal substituent led to a complete ground state recovery within 150 ps indicating the strong influence of the Fe moiety.

Dedicated to Professor Hansgeorg Schnöckel on the occasion of his 80th birthdayWe present new insights into the ligand strength of the metalloid [Ge 9 (Hyp) 3 ] À cluster (Hyp = Si(SiMe 3 ) 3 ) alongside novel neutral Ge 9 clusters of the composition R 3 PAuGe 9 (Hyp) 3 (R=Et, n Pr, i Pr, n Bu, t Bu, Cy). These clusters are synthesized in good yields from KGe 9 (Hyp) 3 and R 3 PAuCl. Further experiments with these new clusters show that the ligand strength of [Ge 9 (Hyp) 3 ] À is in between aryl and alkyl phosphines.

We present a comprehensive femtosecond (fs) transient absorption study of the [Ge9(Hyp)3]− (Hyp = Si(SiMe3)3) cluster solvated in tetrahydrofuran (THF) with special emphasis on intra- and intermolecular charge transfer mechanisms which can be tuned by exchange of the counterion and by dimerization of the cluster. The examination of the visible and the near infrared (NIR) spectral range reveals four different processes of cluster dynamics after UV (267/258 nm) photoexcitation related to charge transfer to solvent and localized excited states in the cluster. The resulting transient absorption is mainly observed in the NIR region. In the UV-Vis range transient absorption of the (neutral) cluster core with similar dynamics can be observed. By transferring concepts of: (i) charge transfer to the solvent known from solvated Na− in THF and (ii) charge transfer in bulk-like materials on metalloid cluster systems containing [Ge9(Hyp)3]− moieties, we can nicely interpret the experimental findings for the different compounds. The first process occurs on a fs timescale and is attributed to localization of the excited electron in the quasi-conduction band/excited state which competes with a charge transfer to the solvent. The latter leads to an excess electron initially located in the vicinity of the parent cluster within the same solvent shell. In a second step, it can recombine with the cluster core with time constants in the picosecond (ps) timescale. Some electrons can escape the influence of the cluster leading to a solvated electron or after interaction with a cation to a contact pair both with lifetimes exceeding our experimentally accessible time window of 1 nanosecond (ns). An additional time constant on a tens of ps timescale is pronounced in the UV-Vis range which can be attributed to the recombination rate of the excited state or quasi conduction band of Ge9−. In the dimer, the excess electron cannot escape the molecule due to strong trapping by the Zn cation that links the two cluster cores.