Non-Resonant Magnetic X-ray Scattering as a Probe of Ultrafast Molecular Spin-State Dynamics: An Ab Initio Theory

With the advancement of high harmonic generation and X-ray free-electron lasers (XFELs) to the attosecond domain, the studies of the ultrafast electron and spin dynamics became possible. Yet, the methods for efficient control and measurement of the quantum state are to be further developed. In this publication, we propose using magnetic X-ray scattering (MXS) for resolving the molecular spin-state dynamics and establish a complete protocol to simulate MXS diffraction patterns in molecules with ab initio quantum chemistry based on the multiconfigurational method. The performance of the method is demonstrated for the simulation of the spin-flip dynamics in the TiCl₄ molecule, initiated by an ultrashort X-ray pulse. The consistent variation of the electron population and the circular dichroic patterns show the capability of MXS to quantitatively detect the spin-state dynamics in real time quantitatively. We also conclude that the spatial shape and extent of the spin density can also be inferred by analyzing the diffraction patterns for randomly oriented and aligned molecules.