Attosecond Monitoring of Nonadiabatic Molecular Dynamics by Transient X-ray Transmission Spectroscopy

Tracing the evolution of molecular coherences can provide a direct, unambiguous probe of nonadiabatic molecular processes, such as the passage through conical intersections of electronic states. Two techniques, attosecond transient absorption spectroscopy (ATAS) and Transient Redistribution of Ultrafast Electronic Coherences in Attosecond Raman Signals (TRUECARS), have been used or proposed for monitoring nonadiabatic molecular dynamics. Both techniques employ the transmission of a weak attosecond extreme-ultraviolet or X-ray probe to interrogate the molecule at controllable time delays with respect to an optical pump, thereby extracting dynamical information from transient spectral features. The connection between these techniques has not been firmly established yet. In this theoretical study, we provide a unified description of both transient transmission techniques, establishing their relationship as limits of the same pump-probe spectroscopy technique for different pulse parameter regimes. We demonstrate this by quantum dynamical simulations of thiophenol photodissociation and show how complementary coherence information can be revealed by the two techniques.