Step-by-step state-selective tracking of fragmentation dynamics of water dications by momentum imaging

The double photoionization of a molecule by one photon ejects two electrons and typically creates an unstable dication. Observing the subsequent fragmentation products in coincidence can reveal a surprisingly detailed picture of the dynamics. Determining the time evolution and quantum mechanical states involved leads to deeper understanding of molecular dynamics. Here in a combined experimental and theoretical study, we unambiguously separate the sequential breakup via D+ + OD+ intermediates, from other processes leading to the same D+ + D+ + O final products of double ionization of water by a single photon. Moreover, we experimentally identify, separate, and follow step by step, two pathways involving the b (1)sigma(+) and a (1)Delta electronic states of the intermediate OD+ ion. Our classical trajectory calculations on the relevant potential energy surfaces reproduce well the measured data and, combined with the experiment, enable the determination of the internal energy and angular momentum distribution of the OD+ intermediate. Determining the time evolution of reactions at the quantum mechanical level improves our understanding of molecular dynamics. Here, authors separate the breakup of water, one bond at a time, from other processes leading to the same final products and experimentally identify, separate, and follow step by step two breakup paths of the transient OD+ fragment.

Automated summary

In this study, the authors successfully separate the sequential breakup pathways in the double ionization of water molecules and experimentally identify, separate, and sequentially track the two fragmentation paths of the intermediate OD+ ion. Determining the time evolution of reactions at the quantum mechanical level is crucial for understanding molecular dynamics.