Filming enhanced ionization in an ultrafast triatomic slingshot.

Filming atomic motion within molecules is an active pursuit of molecular physics and quantum chemistry. A promising method is laser-induced Coulomb Explosion Imaging (CEI) where a laser pulse rapidly ionizes many electrons from a molecule, causing the remaining ions to undergo Coulomb repulsion. The ion momenta are used to reconstruct the molecular geometry which is tracked over time (i.e., filmed) by ionizing at an adjustable delay with respect to the start of interatomic motion. Results are distorted, however, by ultrafast motion during the ionizing pulse. We studied this effect in water and filmed the rapid "slingshot" motion that enhances ionization and distorts CEI results. Our investigation uncovered both the geometry and mechanism of the enhancement which may inform CEI experiments in many other polyatomic molecules.

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 1Σ+ and a 1Δ 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.

Energy of the quasi-free electron in CO and HD: Probing intermolecular potentials within the local Wigner-Seitz model.

We present the quasi-free electron energy V0(ρ) in the weakly polar fluids CO and HD from gas to liquid densities ρ, on noncritical isotherms, and at a temperature near the critical isotherm. These results represent the first systematic investigation of V0(ρ) in polar fluids across a broad density range and illustrate that field enhanced photoemission can be used to obtain data in such systems. We show that the local Wigner-Seitz model for V0(ρ), when coupled with thermodynamic data for the fluids, can yield optimized intermolecular potential parameters, as well as the magnitude of the zero kinetic energy electron scattering length.

Energy of the quasi-free electron in H2, D2, and O2: Probing intermolecular potentials within the local Wigner-Seitz model.

We present for the first time the quasi-free electron energy V0(ρ) for H2, D2, and O2 from gas to liquid densities, on noncritical isotherms and on a near critical isotherm in each fluid. These data illustrate the ability of field enhanced photoemission (FEP) to determine V0(ρ) accurately in strongly absorbing fluids (e.g., O2) and fluids with extremely low critical temperatures (e.g., H2 and D2). We also show that the isotropic local Wigner-Seitz model for V0(ρ)--when coupled with thermodynamic data for the fluid--can yield optimized parameters for intermolecular potentials, as well as zero kinetic energy electron scattering lengths.