Refine
Has Fulltext
- no (5) (remove)
Year of publication
- 2019 (5) (remove)
Language
- English (5)
Is part of the Bibliography
- yes (5)
Keywords
Institute
The phase diagram of water harbors controversial views on underlying structural properties of its constituting molecular moieties, its fluctuating hydrogen-bonding network, as well as pair-correlation functions. In this work, long energy-range detection of the X-ray absorption allows us to unambiguously calibrate the spectra for water gas, liquid, and ice by the experimental atomic ionization cross-section. In liquid water, we extract the mean value of 1.74 +/- 2.1% donated and accepted hydrogen bonds per molecule, pointing to a continuous-distribution model. In addition, resonant inelastic X-ray scattering with unprecedented energy resolution also supports continuous distribution of molecular neighborhoods within liquid water, as do X-ray emission spectra once the femtosecond scattering duration and proton dynamics in resonant X-ray-matter interaction are taken into account. Thus, X-ray spectra of liquid water in ambient conditions can be understood without a two-structure model, whereas the occurrence of nanoscale-length correlations within the continuous distribution remains open.
Charge-density rearrangements after metal-to-ligand charge-transfer excitation in an iron photosensitizer are investigated by R. M Jay, A. Fohlisch et al. in their Communication (DOI: 10.1002/anie.201904761). By using time-resolved X-ray absorption spectroscopy, surprising covalency-effects are revealed that inhibit charge-separation at the intra-molecular level. Furthermore, the underlying mechanism is proposed to be generally in effect for all commonly used photosensitizers in light-harvesting applications, which challenges the common perception of electronic charge-transfer.
Local probes of the electronic ground state are essential for understanding hydrogen bonding in aqueous environments. When tuned to the dissociative core-excited state at the O1s pre-edge of water, resonant inelastic X-ray scattering back to the electronic ground state exhibits a long vibrational progression due to ultrafast nuclear dynamics. We show how the coherent evolution of the OH bonds around the core-excited oxygen provides access to high vibrational levels in liquid water. The OH bonds stretch into the long-range part of the potential energy curve, which makes the X-ray probe more sensitive than infra-red spectroscopy to the local environment. We exploit this property to effectively probe hydrogen bond strength via the distribution of intramolecular OH potentials derived from measurements. In contrast, the dynamical splitting in the spectral feature of the lowest valence-excited state arises from the short-range part of the OH potential curve and is rather insensitive to hydrogen bonding.
We predict the recoil-induced molecular dissociation in hard-x-ray photoionization. The recoil effect is caused by electronic and photon momentum exchange with the molecule. We show the strong role of relativistic effects for the studied molecular fragmentation. The recoil-induced fragmentation of the molecule is caused by elongation of the bond due to the vibrational recoil effect and because of the centrifugal force caused by the rotational recoil. The calculations of the x-ray photoelectron spectra of the H-2 and NO molecules show that the predicted effects can be observed in high-energy synchrotrons like SOLEIL, SPring-8, PETRA, and XFEL SACLA. The relativistic effect enhances the recoil momentum transfer and makes it strongly sensitive to the direction of ejection of the fast photoelectron with respect to the photon momentum.