Directly imaging excited state-resolved transient structures of water induced by valence and inner-shell ionisation

Real-time imaging of transient structure of the electronic excited state is fundamentally critical to understand and control ultrafast molecular dynamics. The ejection of electrons from the inner-shell and valence level can lead to the population of different excited states, which trigger manifold ultrafast relaxation processes, however, the accurate imaging of such electronic state-dependent structural evolutions is still lacking. Here, by developing the laser-induced electron recollision-assisted Coulomb explosion imaging approach and molecular dynamics simulations, snapshots of the vibrational wave-packets of the excited (A) and ground states (X) of D₂O⁺ are captured simultaneously with sub-10 picometre and few-femtosecond precision. We visualise that θ_DOD and R_OD are significantly increased by around 50^∘ and 10 pm, respectively, within approximately 8 fs after initial ionisation for the A state, and the R_OD further extends 9 pm within 2 fs along the ground state of the dication in the present condition. Moreover, the R_OD can stretch more than 50 pm within 5 fs along autoionisation state of dication. The accuracies of the results are limited by the simulations. These results provide comprehensive structural information for studying the fascinating molecular dynamics of water, and pave the way towards to make a movie of excited state-resolved ultrafast molecular dynamics and light-induced chemical reaction.