Time-dependent Hole States in Multiconfigurational Time-Dependent Hartree-Fock Approaches: Applications in Photoionization of Water Molecule

By simulating the real-time multielectron wavefunction with the multi-configurational time-dependent Hartree-Fock (MCTDHF) approach, we conduct an $\mathit{\text{ab}}\mathit{\text{initio}}$ study of the single-photon ionization process of a body-fixed water molecule (${\mathrm{H}}_2\mathrm{O}$) driven by attosecond pulses. To this end, we present a full-dimensional implementation of the MCTDHF method based on one-center expansions, allowing for the simulation of arbitrarily polarized lasers and multi-center polyatomic potentials. With a rigorous definition of the time-dependent hole state (TDHS) using the time-domain generalization of extended Koopmans’ theorem (TD-EKT), we derive the reduced ion density matrix within the MCTDHF framework, which inherently encodes the total and channel-resolved photoionization cross sections of ${\mathrm{H}}_2\mathrm{O}$. The cross sections obtained are benchmarked against existing experimental and theoretical results, validating the TDHS formalism. Furthermore, by adjusting the phase delay and intensity ratio of a pair of orthogonally polarized attosecond pulses, we explore the ultrafast control of attosecond coherence between electronic states of ${\mathrm{H}}_2{\mathrm{O}}^{+}$.