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- anti-Stokes resonant x-ray raman scattering (1)
- binaries: close (1)
- excited state selectivity (1)
- free electron lasers (1)
- resonant inelastic x-ray scattering (1)
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Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion(1,2). Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site(3-11) that need to be controlled to optimize complexes for photocatalytic hydrogen production(8) and selective carbon-hydrogen bond activation(9-11). An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond-resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe(CO)(5) in solution, that the photo-induced removal of CO generates the 16-electron Fe(CO)(4) species, a homogeneous catalyst(12,13) with an electron deficiency at the Fe centre(14,15), in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe(CO)(5) (refs 4, 16-20), was made possible by the ability of femtosecond X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes.
Aims. Recent magnetic field surveys in O- and B-type stars revealed that about 10% of the core-hydrogen-burning massive stars host large-scale magnetic fields. The physical origin of these fields is highly debated. To identify and model the physical processes responsible for the generation of magnetic fields in massive stars, it is important to establish whether magnetic massive stars are found in very young star-forming regions or whether they are formed in close interacting binary systems.
Methods. In the framework of our ESO Large Program, we carried out low-resolution spectropolarimetric observations with FORS 2 in 2013 April of the three most massive central stars in the Trifid nebula, HD 164492A, HD 164492C, and HD 164492D. These observations indicated a strong longitudinal magnetic field of about 500-600 G in the poorly studied component HD 164492C. To confirm this detection, we used HARPS in spectropolarimetric mode on two consecutive nights in 2013 June.
Results. Our HARPS observations confirmed the longitudinal magnetic field in HD 164492C. Furthermore, the HARPS observations revealed that HD 164492C cannot be considered as a single star as it possesses one or two companions. The spectral appearance indicates that the primary is most likely of spectral type B1-B1.5 V. Since in both observing nights most spectral lines appear blended, it is currently unclear which components are magnetic. Long-term monitoring using high-resolution spectropolarimetry is necessary to separate the contribution of each component to the magnetic signal. Given the location of the system HD 164492C in one of the youngest star formation regions, this system can be considered as a Rosetta Stone for our understanding of the origin of magnetic fields in massive stars.
Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics
(2016)
Ultrafast electronic and structural dynamics of matter govern rate and selectivity of chemical reactions, as well as phase transitions and efficient switching in functional materials. Since x-rays determine electronic and structural properties with elemental, chemical, orbital and magnetic selectivity, short pulse x-ray sources have become central enablers of ultrafast science. Despite of these strengths, ultrafast x-rays have been poor at picking up excited state moieties from the unexcited ones. With time-resolved anti-Stokes resonant x-ray Raman scattering (AS-RXRS) performed at the LCLS, and ab initio theory we establish background free excited state selectivity in addition to the elemental, chemical, orbital and magnetic selectivity of x-rays. This unparalleled selectivity extracts low concentration excited state species along the pathway of photo induced ligand exchange of Fe(CO)(5) in ethanol. Conceptually a full theoretical treatment of all accessible insights to excited state dynamics with AS-RXRS with transform-limited x-ray pulses is given-which will be covered experimentally by upcoming transform-limited x-ray sources.
A setup for resonant inelastic soft x-ray scattering on liquids at free electron laser light sources
(2012)
We present a flexible and compact experimental setup that combines an in vacuum liquid jet with an x-ray emission spectrometer to enable static and femtosecond time-resolved resonant inelastic soft x-ray scattering (RIXS) measurements from liquids at free electron laser (FEL) light sources. We demonstrate the feasibility of this type of experiments with the measurements performed at the Linac Coherent Light Source FEL facility. At the FEL we observed changes in the RIXS spectra at high peak fluences which currently sets a limit to maximum attainable count rate at FELs. The setup presented here opens up new possibilities to study the structure and dynamics in liquids.