The last two decades have seen rapid developments in short-pulse x-ray sources, which have enabled the study of chemical dynamics by x-ray spectroscopies with unprecedented sensitivity to nuclear and electronic degrees of freedom on all relevant time scales. In this perspective, some of the major achievements in the study of chemical dynamics with x-ray pulses produced by high-harmonic, free-electron-laser and synchrotron sources on time scales from attoseconds to nanoseconds are reviewed. Major advantages of x-ray spectral probing of chemical dynamics are unprecedented time resolution, element and oxidation state specificity and-depending on the type of x-ray spectroscopy-sensitivity to both the electronic and nuclear structure of the investigated chemical system. Particular dynamic processes probed by x-ray radiation, which are highlighted in this perspective, are the measurement of electronic coherences on attosecond to femtosecond time scales, time-resolved spectroscopy of chemical reactions such as dissociations and pericyclic ring-openings, spin-crossover dynamics, ligand-exchange dynamics, and structural deformations in excited states. X-ray spectroscopic probing of chemical dynamics holds great promise for the future due to the ongoing developments of new types of x-ray spectroscopies such as four-wave mixing and the continuous improvements of the emerging laboratory-based high-harmonic sources, and large-scale facility-based free-electron lasers.

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 1020 cm−3. Separate electron and hole relaxation times are observed as a function of hot carrier energies. A first-order electron and hole decay of ∼1 ps suggests a Shockley–Read–Hall recombination mechanism. The simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions.

Light beams carrying a point singularity with a screw-type phase distribution are associated with an optical vortex. The corresponding momentum flow leads to an orbital angular momentum of the photons 1-3 . The study of optical vortices has led to applications such as particle micro-manipulation 4,5 , imaging 6 , interferometry 7 , quantum information 8 and highresolution microscopy and lithography 9 . Recent analyses showed that transitions forbidden by selection rules seem to be allowed when using optical vortex beams 10 . To exploit these intriguing new applications, it is often necessary to shorten the wavelength by nonlinear frequency conversion. However, during the conversion the optical vortices tend to break up 11-13 . Here we show that optical vortices can be generated in the extreme ultraviolet (XUV) region using high-harmonic generation 14,15 . The singularity impressed on the fundamental beam survives the highly nonlinear process. Vortices in the XUV region have the same phase distribution as the driving field, which is in contradiction to previous findings 16 , where multiplication of the momentum by the harmonic order is expected. This approach opens the way for several applications based on vortex beams in the XUV region.Places where physical quantities become infinite or change abruptly are called singularities. The presence of phase dislocations (singularities) in the wavefront of a light beam determines both the phase and intensity structure around them. As the phase becomes indeterminate at singularities, both the real and the imaginary parts of the field amplitude (that is, also the field intensity) vanish. The characteristic helical phase profiles of optical vortices are described by exp(imθ) multipliers, where θ is the azimuthal coordinate and the integer number m is their topological charge, also called dislocation strength or winding number.Recalling the fact that in free space the Poynting vector gives the momentum flow, for helical phase fronts the Poynting vector has an azimuthal component that produces an orbital angular momentum parallel to the axis of the beam. The momentum circulates around the beam axis, so such beams are said to contain an optical vortex. As has been shown 1-3 , an m-fold charged optical vortex beam carries an orbital angular momentum of mh per photon independent of the spin angular momentum (that is, the polarization state). It was shown that transitions that are forbidden by known selection rules in the electric and magnetic dipole approximation seem to be allowed when using optical vortex beams 10 . This provides a new degree of freedom in the spectroscopy of forbidden transitions. Multi-coloured optical vortices can be generated through a nonlinear frequency-conversion process such as second-harmonic generation 16 or four-wave mixing, which is an important process in the white-light vortex generation. However, as predicted in ref. 11 and observed in ref. 12, vortex breakup in self-focusing nonlinear media is an important issue for supercontinuum vortex genera...

The thermalization of hot carriers and phonons gives direct insight into the scattering processes that mediate electrical and thermal transport. Obtaining the scattering rates for both hot carriers and phonons currently requires multiple measurements with incommensurate timescales. Here, transient extreme-ultraviolet (XUV) spectroscopy on the silicon 2p core level at 100 eV is used to measure hot carrier and phonon thermalization in Si(100) from tens of femtoseconds to 200 ps, following photoexcitation of the indirect transition to the Δ valley at 800 nm. The ground state XUV spectrum is first theoretically predicted using a combination of a single plasmon pole model and the Bethe-Salpeter equation with density functional theory. The excited state spectrum is predicted by incorporating the electronic effects of photo-induced state-filling, broadening, and band-gap renormalization into the ground state XUV spectrum. A time-dependent lattice deformation and expansion is also required to describe the excited state spectrum. The kinetics of these structural components match the kinetics of phonons excited from the electron-phonon and phonon-phonon scattering processes following photoexcitation. Separating the contributions of electronic and structural effects on the transient XUV spectra allows the carrier population, the population of phonons involved in inter- and intra-valley electron-phonon scattering, and the population of phonons involved in phonon-phonon scattering to be quantified as a function of delay time.