frontier-orbital interactions with atom specificity. We anticipate that the method will be broadly applicable in the chemical sciences, and complement approaches that probe structural dynamics in ultrafast processes.In our experimental set-up (Figure 1a), the valence electronic structure of Fe(CO) 5 is probed with femtosecond-resolution resonant inelastic x-ray scattering (RIXS) at the Fe L 3 -edge (Fe experiments. This triplet arises from a singlet state with a time constant of 300 fs, consolidating the notion 6 that sub-ps intersystem crossing appears to be common in the excited-state dynamics of transition-metal complexes 7,[22][23][24] . The persistence of the triplet Fe(CO) 4 ( 3 B 2 ) up to our maximum time delay of 3 ps is consistent with it undergoing a slow, spin-forbidden reaction with intersystem crossing to a solvent-complexed singlet state on the 50-100 ps time scale 4,5, 25 . However, the observed branching on a sub-ps time scale into the competing and simultaneous reaction channels of spin crossover and ligation to form coordinatively saturated species introduces an efficient pathway circumventing this spin barrier. It also supports the idea that the high density of electronic excited states and the relatively large amount of excess energy available in the system determine the course of the excited-state dynamics, rather than spin selection rules alone 5,6 . Fast ligation could be facilitated along the singlet pathway, confirming the general notion that solvent-stabilized metal centers form fast 3, 4, 11 and consistent with the observation of unsaturated carbonyl Cr(CO) 5 forming a solvent complex in alcohol solution within 1.6 ps 26 . An alternative proposal 20 for Fe(CO) 5 involves concerted exchange of CO and EtOH on the time scale of ligand dissociation of 100-150 fs. This would also proceed along a singlet pathway and in agreement with our results, as the temporal resolution of our measurements is not sufficient to distinguish between this concerted and the alternative sequential process. Revealing in detail 8 the influence of solvent-solute interactions will have to be the subject of future studies, which could also explore whether the structure of the solute prior to dissociation 20 influences the excited-state branching ratio between the different pathways.We find that the ligation capability of Fe(CO) 4 is mostly determined by its d σ * LUMO, which receives σ donation from occupied CO or ethanol ligand orbitals. Population of the antibonding d σ * orbital in excited singlet ( 1 B 2 ) and triplet ( 3 B 2 ) Fe(CO) 4 impedes σ donation from ligands (see sketches in Figure 3), explaining the inertness of these species against ligation; this problem is absent in the ligation channel that produces coordinately saturated species. Establishing this correlation of orbital symmetry with spin multiplicity and reactivity 27 is enabled by the atom specificity with which x-ray laser based femtosecondresolution spectroscopy can explore frontier-orbital interactions. This ability gives unique access t...

Dynamical processes are commonly investigated using laser pump-probe experiments, with a pump pulse exciting the system of interest and a second probe pulse tracking its temporal evolution as a function of the delay between the pulses. Because the time resolution attainable in such experiments depends on the temporal definition of the laser pulses, pulse compression to 200 attoseconds (1 as = 10(-18) s) is a promising recent development. These ultrafast pulses have been fully characterized, and used to directly measure light waves and electronic relaxation in free atoms. But attosecond pulses can only be realized in the extreme ultraviolet and X-ray regime; in contrast, the optical laser pulses typically used for experiments on complex systems last several femtoseconds (1 fs = 10(-15) s). Here we monitor the dynamics of ultrafast electron transfer--a process important in photo- and electrochemistry and used in solid-state solar cells, molecular electronics and single-electron devices--on attosecond timescales using core-hole spectroscopy. We push the method, which uses the lifetime of a core electron hole as an internal reference clock for following dynamic processes, into the attosecond regime by focusing on short-lived holes with initial and final states in the same electronic shell. This allows us to show that electron transfer from an adsorbed sulphur atom to a ruthenium surface proceeds in about 320 as.

Femtosecond time-resolved core-level photoemission spectroscopy with a free-electron laser is used to measure the atomic-site specific charge-order dynamics in the charge-density-wave/Mott insulator 1T -TaS2. After strong photoexcitation, a prompt loss of charge order and subsequent fast equilibration dynamics of the electron-lattice system are observed. On the time scale of electron-phonon thermalization, about 1 ps, the system is driven across a phase transition from a long-range charge ordered state to a quasi-equilibrium state with domain-like short-range charge and lattice order. The experiment opens the way to study the nonequilibrium dynamics of condensed matter systems with full elemental, chemical, and atomic site selectivity.Femtosecond time-resolved spectroscopy has become a powerful tool in condensed matter research because it delivers direct dynamical information at the fundamental time scale of elementary electronic processes [1,2]. The method is particularly useful for complex materials, in which two or more of the lattice, charge, spin, and orbital degrees of freedom are strongly coupled. It allows to determine the nature and strength of the interactions between the degrees of freedom, to identify the dominant interactions, and thus to gain important insights into ground-state properties, thermally driven phase transitions, and, possibly, novel hidden phases [3][4][5][6].An exceedingly fertile ground for the combination of spectral selectivity and femtosecond time resolution has been found in materials, in which the charge and lattice degrees of freedom interact strongly to form a coupled charge-density-wave (CDW)/periodic-latticedistortion (PLD) ground state. The quasiparticle and collective mode dynamics of the CDW/PLD state, the finite electron-lattice coupling time, and the collapse of the electronic gap under strong excitation are now known [4][5][6][7][8][9]. Yet, direct dynamical information on the CDW itself, i.e., on the local charge order, is missing. Specifically, it is not clear how fast a CDW can melt and recondense after impulsive excitation. The present study provides this fundamental piece of information for the layered ref-Employing time-resolved x-ray photoemission spectroscopy (TR-XPS) with a free-electron laser [12,13], we directly measure the melting of a large-amplitude CDW in 1T -TaS 2 at atomic sites in real time. Our results show that long-range charge order collapses promptly after strong optical excitation and that a domain-like quasi-equilibrium CDW/PLD state is reached with a subpicosecond time constant.The model system 1T -TaS 2 is a complex material with a simple basic structure consisting of S-Ta-S sandwiches in which each Ta atom is octahedrally coordinated by six S atoms. The interesting physics in this compound is restricted to the hexagonal Ta layers and results from simultaneously strong electron-phonon and electron-electron interactions. The phase diagram includes a high-temperature metallic phase, incommensurate CDW and nearly commensurate CDW (NCCDW) phases...

Inelastic x-ray scattering spectra excited at the 1s(-1)π* resonance of gas phase O2 have been recorded with an overall energy resolution that allows for well-resolved vibrational progressions. The nuclear wave packet dynamics in the intermediate state is reflected in vibrational excitations of the electronic ground state, and by fine-tuning the excitation energy the dissociation dynamics in the predissociative B'(3)Πg final state is controlled.

The new instrument for near-ambient-pressure X-ray photoelectron spectroscopy which has been installed at the MAX II ring of the Swedish synchrotron radiation facility MAX IV Laboratory in Lund is presented. The new instrument, which is based on a SPECS PHOIBOS 150 NAP analyser, is the first to feature the use of retractable and exchangeable high-pressure cells. This implies that clean vacuum conditions are retained in the instrument's analysis chamber and that it is possible to swiftly change between near-ambient and ultrahigh-vacuum conditions. In this way the instrument implements a direct link between ultrahigh-vacuum and in situ studies, and the entire pressure range from ultrahigh-vacuum to near-ambient conditions is available to the user. Measurements at pressures up to 10 À5 mbar are carried out in the ultrahighvacuum analysis chamber, while measurements at higher pressures are performed in the high-pressure cell. The installation of a mass spectrometer on the exhaust line of the reaction cell offers the users the additional dimension of simultaneous reaction data monitoring. Moreover, the chosen design approach allows the use of dedicated cells for different sample environments, rendering the Swedish ambient-pressure X-ray photoelectron spectroscopy instrument a highly versatile and flexible tool.Keywords: ambient-pressure X-ray photoelectron spectroscopy; high-pressure X-ray photoelectron spectroscopy; X-ray photoelectron spectroscopy; in situ; operando; catalysis.

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Amorphous materials represent a large and important emerging area of material's science. Amorphous oxides are key technological oxides in applications such as a gate dielectric in Complementary metal-oxide semiconductor devices and in Silicon-Oxide-NitrideOxide-Silicon and TANOS (TaN-Al 2 O 3 -Si 3 N 4 -SiO 2 -Silicon) flash memories. These technologies are required for the high packing density of today's integrated circuits. Therefore the investigation of defect states in these structures is crucial. In this work we present X-ray synchrotron measurements, with an energy resolution which is about 5-10 times higher than is attainable with standard spectrometers, of amorphous alumina. We demonstrate that our experimental results are in agreement with calculated spectra of amorphous alumina which we have generated by stochastic quenching. This first principles method, which we have recently developed, is found to be superior to molecular dynamics in simulating the rapid gas to solid transition that takes place as this material is deposited for thin film applications. We detect and analyze in detail states in the band gap that originate from oxygen pairs. Similar states were previously found in amorphous alumina by other spectroscopic methods and were assigned to oxygen vacancies claimed to act mutually as electron and hole traps. The oxygen pairs which we probe in this work act as hole traps only and will influence the information retention in electronic devices. In amorphous silica oxygen pairs have already been found, thus they may be a feature which is characteristic also of other amorphous metal oxides.stochastic quench | X-ray absorption spectroscopy | ab initio | coating D espite early attempts to describe the fundamental electronic properties of noncrystalline semiconductors (1-5), experimental and theoretical knowledge of localized states in the gap of amorphous semiconductors and insulators is still limited. General features of the electronic structure of amorphous semiconductors are quite well known, such as the broad distribution of coordinations and the lack of long range order that induces valence and conduction band tails in the band gap (6). However, the origin of these states is less explored experimentally (7,8) and theoretical investigations are mainly limited to the crystalline polymorphs (9-11). Amorphous Alumina (am-Al 2 O 3 ) is currently one of the key technological amorphous materials, where one promising application of am-Al 2 O 3 is as a high-k dielectric in transistors (12). The use of am-Al 2 O 3 in TANOS (TaN-Al 2 O 3 -Si 3 N 4 -SiO 2 -Silicon) flash memories, which are currently investigated for gigabite and terabite scale flash memories, puts even higher demands on alumina as a current-blocking high-k dielectric.From optical absorption and photoluminescence, states related to F-centers (9, 10) and impurities have been identified in the band gap of am-Al 2 O 3 down to 3.18 and 3.25 eV relative to the valence band edge (13,14). In another study, electronbeam induced states in the am-Al ...

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