We present a static and picosecond X-ray absorption study at the Cu K-edge of bis(2,9-dimethyl-1,10-phenanthroline)copper(I) ([Cu(dmp)2](+); dmp = 2,9-dimethyl-1,10-phenanthroline) dissolved in acetonitrile and dichloromethane. The steady-state photoluminescence spectra in dichloromethane and acetonitrile are also presented and show a shift to longer wavelengths for the latter, which points to a stronger stabilization of the excited complex. The fine structure features of the static and transient X-ray spectra allow an unambiguous assignment of the electronic and geometric structure of the molecule in both its ground and excited (3)MLCT states. Importantly, the transient spectra are remarkably similar for both solvents, and the spectral changes can be rationalized using the optimized ground- and excited-state structures of the complex. The proposed assignment of the lifetime shortening of the excited state in donor solvents (acetonitrile) to a metal-centered exciplex is not corroborated here. Molecular dynamics simulations confirm the lack of complexation; however, in both solvents the molecules come close to the metal but undergo rapid exchange with the bulk. The shortening of the lifetime of the title complex and nine additional related complexes can be rationalized by the decrease in the (3)MLCT energy. Deviations from this trend may be explained by means of the effects of the dihedral angle between the ligand planes, the solvent, and the (3)MLCT-(1)MLCT energy gap.
Titanium dioxide (TiO2) is the most popular material for applications in solar-energy conversion and photocatalysis, both of which rely on the creation, transport, and trapping of charges (holes and electrons). The nature and lifetime of electron traps at room temperature have so far not been elucidated. Herein, we use picosecond X-ray absorption spectroscopy at the Ti K-edge and the Ru L3-edge to address this issue for photoexcited bare and N719-dye-sensitized anatase and amorphous TiO2 nanoparticles. Our results show that 100 ps after photoexcitation, the electrons are trapped deep in the defect-rich surface shell in the case of anatase TiO2, whereas they are inside the bulk in the case of amorphous TiO2. In the case of dye-sensitized anatase or amorphous TiO2, the electrons are trapped at the outer surface. Only two traps were identified in all cases, with lifetimes in the range of nanoseconds to tens of nanoseconds.
The SwissFEL X-ray Free Electron Laser (XFEL) facility started construction at the Paul Scherrer Institute (Villigen, Switzerland) in 2013 and will be ready to accept its first users in 2018 on the Aramis hard X-ray branch. In the following sections we will summarize the various aspects of the project, including the design of the soft and hard X-ray branches of the accelerator, the results of SwissFEL performance simulations, details of the photon beamlines and experimental stations, and our first commissioning results.
Nanostructures of transition metal oxides, such as zinc oxide, have attracted considerable interest for solar-energy conversion and photocatalysis. Both applications are sensitive to the transport and trapping of photoexcited charge carriers. The probing of electron trapping has recently become possible using time-resolved element-sensitive methods, such as X-ray spectroscopy. However, valence-band-trapped holes have so far escaped observation. Herein we use X-ray absorption spectroscopy combined with a dispersive X-ray emission spectrometer to probe the charge carrier relaxation and trapping processes in zinc oxide nanoparticles after above band-gap photoexcitation. Our results, supported by simulations, demonstrate that within 80 ps, photoexcited holes are trapped at singly charged oxygen vacancies, which causes an outward displacement by ~15% of the four surrounding zinc atoms away from the doubly charged vacancy. This identification of the hole traps provides insight for future developments of transition metal oxide-based nanodevices.
Femtosecond time-resolved X-ray diffraction is used to study a photo-induced phase transition between two charge density wave (CDW) states in 1T-TaS2, namely the nearly commensurate (NC) and the incommensurate (I) CDW states. Structural modulations associated with the NC-CDW order are found to disappear within 400 fs. The photo-induced I-CDW phase then develops through a nucleation/growth process which ends 100 ps after laser excitation. We demonstrate that the newly formed I-CDW phase is fragmented into several nanometric domains that are growing through a coarsening process. The coarsening dynamics is found to follow the universal Lifshitz-Allen-Cahn growth law, which describes the ordering kinetics in systems exhibiting a non-conservative order parameter.Among strongly correlated electron systems, superconductors and materials exhibiting metal-insulator transitions are usually characterized by strong electronelectron and electron-phonon couplings [1][2][3]. At thermodynamic equilibrium, the corresponding many-body interactions lead to rich phase diagrams as a function of temperature, pressure or doping. Such compounds also display fascinating out-of-equilibrium physics, in the form of ultra-fast symmetry changes known as photoinduced phase transitions [4][5][6], and occurrence of new, transient states [6][7][8].Charge density wave (CDW) states are broken symmetry states of metals arising from electron-phonon interactions. They are characterized by a periodic modulation of both atomic positions and electron density. The metal-to-CDW phase transition is characterized by the growth of a complex-valued order parameter p = A exp iΦ , which reflects both the amplitude A and the phase Φ of the periodic modulation [3]. A number of photo-induced phase transitions that have been achieved in CDW compounds correspond to a suppression of the CDW order, i.e. a transition between a CDW state and a metallic state free of any structural modulation [5,[9][10][11][12][13][14][15]. Among those, the photo-induced suppression of the CDW state in blue bronze was shown to involve a coherent motion of atoms along the normal coordinates of the CDW amplitude mode [5]. In this case, the amplitude mode allows continuous variations of the modulus of the order parameter |p|, the metallic state corresponding to |p|=0. In the present work, we focus on the photo-induced phase transition between the nearly commensurate (NC) and the incommensurate (I) CDW states in 1T-TaS 2 , which exhibit two distinct order parameters. When thermallyinduced, this first-order phase transition involves a discontinuous change of atomic positions, and a coexistence of NC and I phase domains over a 3 K range [16,17]. It is thus expected that the photo-induced I phase appears through non-coherent atomic motions, by a nucleation/growth process. We report that the photo-induced NC → I phase is completed within 100 ps after laser excitation. At this 100 ps delay, the photo-induced I-CDW phase is found divided into domains with a typical size of 150Å. Its ordering kinet...
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