Vandana Sharma

Observing the creation of electronic feshbach resonances in soft x-ray-induced O2 dissociation.

When an atom or molecule is ionized by an x-ray, highly excited states can be created that then decay, or autoionize, by ejecting a second electron from the ion. We found that autoionization after soft x-ray photoionization of molecular oxygen follows a complex multistep process. By interrupting the autoionization process with a short laser pulse, we showed that autoionization cannot occur until the internuclear separation of the fragments is greater than approximately 30 angstroms. As the ion and excited neutral atom separated, we directly observed the transformation of electronically bound states of the molecular ion into Feshbach resonances of the neutral oxygen atom that are characterized by both positive and negative binding energies. States with negative binding energies have not previously been predicted or observed in neutral atoms.

Visualizing electron rearrangement in space and time during the transition from a molecule to atoms

Imaging and controlling reactions in molecules and materials at the level of electrons is a grand challenge in science, relevant to our understanding of charge transfer processes in chemistry, physics, and biology, as well as material dynamics. Direct access to the dynamic electron density as electrons are shared or transferred between atoms in a chemical bond would greatly improve our understanding of molecular bonding and structure. Using reaction microscope techniques, we show that we can capture how the entire valence shell electron density in a molecule rearranges, from molecular-like to atomic-like, as a bond breaks. An intense ultrashort laser pulse is used to ionize a bromine molecule at different times during dissociation, and we measure the total ionization signal and the angular distribution of the ionization yield. Using this technique, we can observe density changes over a surprisingly long time and distance, allowing us to see that the electrons do not localize onto the individual Br atoms until the fragments are far apart (∼5.5 Å), in a region where the potential energy curves for the dissociation are nearly degenerate. Our observations agree well with calculations of the strong-field ionization rates of the bromine molecule.

Direct Measurement of the Angular Dependence of the Single-Photon Ionization of Aligned N2 and CO2 †

By combining a state-of-the-art high-harmonic ultrafast soft X-ray source with field-free dynamic alignment, we map the angular dependence of molecular photoionization yields for the first time for a nondissociative molecule. The observed modulation in ion yield as a function of molecular alignment is attributed to the molecular frame transition dipole moment of single-photon ionization to the X, A and B states of N2(+) and CO2(+). Our data show that the transition dipoles for single-photon ionization of N2 and CO2 at 43 eV have larger perpendicular components than parallel ones. A direct comparison with published theoretical partial wave ionization cross-sections confirms these experimental observations, which are the first results to allow such comparison with theory for bound cation states. The results provide the first step toward a novel method for measuring molecular frame transition dipole matrix elements.

Visualizing Electron Rearrangement in Space and Time during the Transition from a Molecule to Atoms

Using strong field ionization and time-resolved reaction microscope techniques, we visualize both in space and time the dynamical evolution of the electrons as a molecular bond ruptures, and discover new aspects to the electronic dynamics.

Direct Measurement of Angle-Dependent Single Photon Ionization of N2 and CO2

We present a novel method for determining the angular dependence of molecular photoionization, by measuring time-dependent ionization yields from transiently aligned molecules. This method allows us to map the angular dependence of nondissociative singlephoton ionization for molecules (N2 and CO2) for the first time.

Autoionization dynamics and Feshbach resonances: Femtosecond EUV study of O2 excitation and dissociation

In this work, we present a time-domain study of the complex, multi-step, evolution of highly excited states of oxygen (O2) that result from EUV photoionization. By monitoring the dissociation of molecular oxygen ions, we show that autoionization cannot occur until the internuclear separation is 30 A or greater. As the ion and excited neutral atom separate, we directly observe the transformation of electronically bound states of the molecular ion into Feshbach resonances of the neutral oxygen atom. We achieve this by using laser high-harmonics in a femtosecond EUV-IR pump-probe scheme, combined with a triple coincidence reaction microscope measurement. Finally, we show control of the dissociation pathway through IR pulse induced ionization.