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Simulation of X-ray transient absorption for following vibrations in coherently ionized F2 molecules
Chemical Physics (2017)
  • Anthony D. Dutoi, University of the Pacific
  • Stephen R. Leone, Lawrence Berkeley National Laboratory
Femtosecond and attosecond X-ray transient absorption experiments are becoming increasingly sophisticated tools for probing nuclear dynamics. In this work, we explore and develop theoretical tools needed for interpretation of such spectra,in order to characterize the vibrational coherences that result from ionizing a molecule in a strong IR field. Ab initio data for F2 is combined with simulations of nuclear dynamics, in order to simulate time-resolved X-ray absorption spectra for vibrational wavepackets after coherent ionization at 0 K and at finite temperature. Dihalogens pose rather difficult electronic structure problems, and the issues encountered in this work will be reflective of those encountered with any core–valence excitation simulation when a bond is breaking. The simulations reveal a strong dependence of the X-ray absorption maximum on the locations of the vibrational wave packets. A Fourier transform of the simulated signal shows features at the overtone frequencies of both the neutral and the cation, which reflect spatial interferences of the vibrational eigenstates. This provides a direct path for implementing ultrafast X-ray spectroscopic methods to visualize coherent nuclear dynamics.
Publication Date
January 12, 2017
Citation Information
Anthony D. Dutoi and Stephen R. Leone. "Simulation of X-ray transient absorption for following vibrations in coherently ionized F2 molecules" Chemical Physics Vol. 482 (2017) p. 249 - 264 ISSN: 0301-0104
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