Density matrix-based time-dependent configuration interaction approach to ultrafast spin-flip dynamics

Abstract

ABSTRACTRecent developments in attosecond spectroscopy yield access to the correlated motion of electrons on their intrinsic timescales. Spin-flip dynamics is usually considered in the context of valence electronic states, where spin–orbit coupling is weak and processes related to the electron spin are usually driven by nuclear motion. However, for core-excited states, where the core-hole has a nonzero angular momentum, spin–orbit coupling is strong enough to drive spin-flips on a much shorter timescale. Using density matrix-based time-dependent restricted active space configuration interaction including spin–orbit coupling, we address an unprecedentedly short spin-crossover for the example of L-edge (2p→3d) excited states of a prototypical Fe(II) complex. This process occurs on a timescale, which is faster than that of Auger decay (∼4 fs) treated here explicitly. Modest variations of carrier frequency and pulse duration can lead to substantial changes in the spin-state yield, suggesting its control by soft X-ray light.