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Abstract An essential problem in photochemistry is understanding the coupling of electronic and nuclear dynamics in molecules, which manifests in processes such as hydrogen migration. Measurements of hydrogen migration in molecules that have more than two equivalent hydrogen sites, however, produce data that is difficult to compare with calculations because the initial hydrogen site is unknown. We demonstrate that coincidence ion-imaging measurements of a few deuterium-tagged isotopologues of ethanol can determine the contribution of each initial-site composition to hydrogen-rich fragments following strong-field double ionization. These site-specific probabilities produce benchmarks for calculations and answer outstanding questions about photofragmentation of ethanol dications; e.g., establishing that the central two hydrogen atoms are 15 times more likely to abstract the hydroxyl proton than a methyl-group proton to form H$${}_{3}^{+}$$ ${}_3^{+}$and that hydrogen scrambling, involving the exchange of hydrogen between different sites, is important in H₂O⁺formation. The technique extends to dynamic variables and could, in principle, be applied to larger non-cyclic hydrocarbons. 

Abstract 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 Σ + and a 1 Δ 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. 

An adaptive learning algorithm coupled with 3D momentum-based feedback is used to identify intense laser pulse shapes that control H 3 + formation from ethane. Specifically, we controlled the ratio of D 2 H + to D 3 + produced from the D 3 C-CH 3 isotopologue of ethane, which selects between trihydrogen cations formed from atoms on one or both sides of ethane. We are able to modify the D 2 H + : D 3 + ratio by a factor of up to three. In addition, two-dimensional scans of linear chirp and third-order dispersion are conducted for a few fourth-order dispersion values while the D 2 H + and D 3 + production rates are monitored. The optimized pulse is observed to influence the yield, kinetic energy release, and angular distribution of the D 2 H + ions while the D 3 + ion dynamics remain relatively stable. We subsequently conducted COLTRIMS experiments on C 2 D 6 to complement the velocity map imaging data obtained during the control experiments and measured the branching ratio of two-body double ionization. Two-body D 3 + + C 2 D 3 + is the dominant final channel containing D 3 + ions, although the three-body D + D 3 + + C 2 D 2 + final state is also observed. 

Abstract We present state-selective measurements on the N H 2 + + H + and NH + + H + + H dissociation channels following single-photon double ionization at 61.5 eV of neutral NH 3 , where the two photoelectrons and two cations are measured in coincidence using 3D momentum imaging. Three dication electronic states are identified to contribute to the N H 2 + + H + dissociation channel, where the excitation in one of the three states undergoes intersystem crossing prior to dissociation, producing a cold N H 2 + fragment. In contrast, the other two states directly dissociate, producing a ro-vibrationally excited N H 2 + fragment with roughly 1 eV of internal energy. The NH + + H + + H channel is fed by direct dissociation from three intermediate dication states, one of which is shared with the N H 2 + + H + channel. We find evidence of autoionization contributing to each of the double ionization channels. The distributions of the relative emission angle between the two photoelectrons, as well as the relative angle between the recoil axis of the molecular breakup and the polarization vector of the ionizing field, are also presented to provide insight on both the photoionization and photodissociation mechanisms for the different dication states.