Quantum electronic coherences by attosecond transient absorption spectroscopy: ab initio B-spline RCS-ADC study

Here I present a fully ab initio time-resolved study of X-ray attosecond transient absorption spectroscopy (ATAS) in a prototypical polyatomic molecule, pyrazine, and demonstrate the possibility of retrieving the many-electron quantum ionic coherences arising in attosecond molecular photoionisation and pre-determining the subsequent charge-directed photochemical reactivity. Advanced first-principles many-electron simulations are performed, within a hybrid XUV pump/X-ray probe setup, to describe the interaction of pyrazine with both XUV pump and X-ray probe pulses, and study the triggered correlated many-electron dynamics. The calculations are carried out by means of the recently-developed ab initio method for many-electron dynamics in polyatomic molecules, the time-dependent (TD) B-spline Restricted Correlation Space-Algebraic Diagrammatic Construction (RCS-ADC). RCS-ADC simulates molecular ionisation from first principles, combining the accurate description of electron correlation of quantum chemistry with the full account of the continuum dynamics of the photoelectron. Complete theoretical characterisation of the atto-ionised many-electron state and photo-induced attosecond charge dynamics is achieved by calculating the reduced ionic density matrix (R-IDM) of the bipartite ion-photoelectron system, with full inclusion of the correlated shakeup states. Deviations from the sudden approximation picture of photoionisation, in the low-photon-energy limit, are presented. The effect of the multi-channel interaction between the parent-ion and the emitted photoelectron on the onset of the quantum electronic coherences is analysed. Moreover, I show how the Schmidt decomposition of the R-IDM unravels the many-electron dynamics triggered by the pump, allowing for the identification of the key channels involved. Finally, I calculate the X-ray attosecond transient absorption spectra of XUV-ionised pyrazine. The results unveil the mapping of the ATAS measurement onto the quantum electronic coherences, and related non-zero R-IDM matrix elements, produced upon ionisation by the XUV pump laser pulse.