Femtosecond x-ray absorption spectroscopy of pyrazine at the nitrogen K-edge: on the validity of the Lorentzian limit

Link:
Autor/in:
Erscheinungsjahr:
2021
Medientyp:
Text
Schlagworte:
  • Lorentzian limit
  • molecule-light interaction
  • multiconfiguration time-dependent Hartree
  • non-adiabatic molecular dynamics
  • short-time approximation
  • transient x-ray absorption spectroscopy
Beschreibung:
  • We calculate the femtosecond x-ray absorption spectrum of pyrazine at the nitrogen K-edge including the wavepacket dynamics in both the valence and core-excited state manifolds. We do not invoke the widely used short-time (or Lorentzian) approximation which neglects the nuclear dynamics after the x-ray probe excitation. Instead, we calculate the x-ray-induced polarization in the time-domain where the optical pump as well as x-ray probe pulses are explicitly described. While the non-adiabatic population transfer following the optical excitation is well reproduced in the Lorentzian limit the transient x-ray absorption spectra obtained under this approximation lack some vibronic features, even when considering the short core-hole lifetime of nitrogen. We further demonstrate the effect of an increasingly longer pulse on the observed photo-triggered wavepacket dynamics which are blurred to the point that the x-ray probe response becomes effectively time-independent.
Lizenz:
  • info:eu-repo/semantics/closedAccess
Quellsystem:
Forschungsinformationssystem der UHH

Interne Metadaten
Quelldatensatz
oai:www.edit.fis.uni-hamburg.de:publications/9b8810da-b4b3-45ba-924c-249f3177c189