Searcharxiv⌕ Search

arXiv subjects

M. Mucke

Publications and source records attributed to M. Mucke.

3 recordsLinked to original sources
arXiv2016

Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption

Organic chromophores with heteroatoms possess an important excited state relaxation channel from an optically allowed ππ* to a dark nπ*state. We exploit the element and site specificity of soft x-ray absorption spectroscopy to selectively follow the electronic change during the ππ*/nπ* internal conversion. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the near edge x-ray absorption fine structure (NEXAFS) spectrum at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept with the nucleobase thymine, a prototypical heteroatomic chromophore. With the help of time resolved NEXAFS spectroscopy at the oxygen K-edge, we unambiguously show that ππ*/nπ* internal conversion takes place within (60 \pm 30) fs. High-level coupled cluster calculations on the isolated molecules used in the experiment confirm the superb electronic structure sensitivity of this new method for excited state investigations.

physics.chem-ph↗
arXiv2016

Machine learning applied to single-shot x-ray diagnostics in an XFEL

X-ray free-electron lasers (XFELs) are the only sources currently able to produce bright few-fs pulses with tunable photon energies from 100 eV to more than 10 keV. Due to the stochastic SASE operating principles and other technical issues the output pulses are subject to large fluctuations, making it necessary to characterize the x-ray pulses on every shot for data sorting purposes. We present a technique that applies machine learning tools to predict x-ray pulse properties using simple electron beam and x-ray parameters as input. Using this technique at the Linac Coherent Light Source (LCLS), we report mean errors below 0.3 eV for the prediction of the photon energy at 530 eV and below 1.6 fs for the prediction of the delay between two x-ray pulses. We also demonstrate spectral shape prediction with a mean agreement of 97%. This approach could potentially be used at the next generation of high-repetition-rate XFELs to provide accurate knowledge of complex x-ray pulses at the full repetition rate.

physics.data-an↗
arXiv2013

Delayed Ultrafast X-ray Auger Probing (DUXAP) of Nucleobase Ultraviolet Photoprotection

We present a new method for ultrafast spectroscopy of molecular photoexcited dynamics. The technique uses a pair of femtosecond pulses: a photoexcitation pulse initiating excited state dynamics followed by a soft x-ray (SXR) probe pulse that core ionizes certain atoms inside the molecule. We observe the Auger decay of the core hole as a function of delay between the photoexcitation and SXR pulses. The core hole decay is particularly sensitive to the local valence electrons near the core and shows new types of propensity rules, compared to dipole selection rules in SXR absorption or emission spectroscopy. We apply the delayed ultrafast x-ray Auger probing (DUXAP) method to the specific problem of nucleobase photoprotection to demonstrate its potential. The ultraviolet photoexcited ππ* states of nucleobases are prone to chemical reactions with neighboring bases. To avoid this, the single molecules funnel the ππ* population to lower lying electronic states on an ultrafast timescale under violation of the Born-Oppenheimer approximation. The new type of propensity rule, which is confirmed by Auger decay simulations, allows us to have increased sensitivity on the direct relaxation from the ππ* state to the vibrationally hot electronic ground state. For the nucleobase thymine, we measure a decay constant of 300 fs in agreement with previous quantum chemical simulations.

physics.chem-ph↗