American Chemical Society
ct7b00920_si_001.pdf (2.51 MB)

Attosecond X‑ray Diffraction Triggered by Core or Valence Ionization of a Dipeptide

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journal contribution
posted on 2017-11-15, 00:00 authored by Daeheum Cho, Jérémy R. Rouxel, Markus Kowalewski, Jin Yong Lee, Shaul Mukamel
With the advancement of intense ultrafast X-ray sources, it is now possible to create a molecular movie by following the electronic dynamics in real time and real space through time-resolved X-ray diffraction. Here we employ real-time time-dependent density functional theory (RT-TDDFT) to simulate the electronic dynamics after an impulse core or valence ionization in the glycine–phenylalanine (GF) dipeptide. The time-evolving dipole moment, the charge density, and the time-resolved X-ray diffraction signals are calculated. The charge oscillation is calculated for 7 fs for valence ionization and 500 as for core ionization. The charge oscillation time scale is comparable to that found in a phenylalanine monomer (4 fs) [Science 2014, 346, 336] and is slightly longer because of the elongated glycine chain. Following valence ionization, the charge migration across the GF is mediated by the delocalized lone-pair orbitals of oxygen and nitrogen of the electron-rich amide group. The temporal Fourier transform of the dipole moment provides detailed information on the charge migration dynamics and the molecular orbitals involved. Heterodyne-detected attosecond X-ray diffraction signals provide the magnitude and phase of the scattering amplitude in momentum space and can thus be inverted to yield the charge density in real space.