Imaging the Temporal Evolution of Molecular Orbitals during Ultrafast Dissociation.

We investigate the temporal evolution of molecular frame angular distributions of Auger electrons emitted during ultrafast dissociation of HCl following a resonant single-photon excitation. The electron emission pattern changes its shape from that of a molecular σ orbital to that of an atomic p state as the system evolves from a molecule into two separated atoms.

Electron diffraction self-imaging of molecular fragmentation in two-step double ionization of water.

We doubly ionize H(2)O by single photon absorption at 43 eV leading to H(+) + OH(+). A direct double ionization and a sequential process in which single ionization is followed by rapid dissociation into a proton and an autoionizing OH(*) are identified. The angular distribution of this delayed autoionization electron shows a preferred emission in the direction of the emitted proton. From this diffraction feature we obtain internuclear distances of 700 to 1100 a.u. at which the autoionization of the OH(*) occurs. The experimental findings are in line with calculations of the excited potential energy surfaces and their lifetimes.

Ionization dynamics of helium dimers in fast collisions with He++.

By employing the cold target recoil ion momentum spectroscopy technique, we have investigated the (He+, He+) breakup of a helium dimer (He2) caused by transfer ionization and double capture in collisions with alpha particles (E = 150 keV/u). Surprisingly, the results show a two-step process as well as a one-step process followed by electron exchange. In addition, interatomic Coulombic decay [L. S. Cederbaum, J. Zobeley, and F. Tarantelli, Phys. Rev. Lett. 79, 4778 (1997).] is observed in an ion collision for the first time.

Imaging of the structure of the argon and neon dimer, trimer, and tetramer.

We Coulomb explode argon and neon dimers, trimers, and tetramers by multiple ionization in an ultrashort 800 nm laser pulse. By measuring all momentum vectors of the singly charged ions in coincidence, we determine the ground state nuclear wave function of the dimer, trimer, and tetramer. Furthermore we retrieve the bond angles of the trimer in position space by applying a classical numerical simulation. For the argon and neon trimer, we find a structure close to the equilateral triangle. The width of the distribution around the equilateral triangle is considerably wider for neon than for argon.

Interatomic Coulombic decay following photoionization of the helium dimer: observation of vibrational structure.

Using synchrotron radiation we simultaneously ionize and excite one helium atom of a helium dimer (He2) in a shakeup process. The populated states of the dimer ion [i.e., He(*+)(n = 2, 3) - He] are found to deexcite via interatomic Coulombic decay. This leads to the emission of a second electron from the neutral site and a subsequent Coulomb explosion. In this Letter we present a measurement of the momenta of fragments that are created during this reaction. The electron energy distribution and the kinetic energy release of the two He+ ions show pronounced oscillations which we attribute to the structure of the vibrational wave function of the dimer ion.

Single photon double ionization of the helium dimer.

We show that a single photon can ionize the two helium atoms of the helium dimer in a distance up to 10 A. The energy sharing among the electrons, the angular distributions of the ions and electrons, as well as comparison with electron impact data for helium atoms suggest a knockoff type double ionization process. The Coulomb explosion imaging of He2 provides a direct view of the nuclear wave function of this by far most extended and most diffuse of all naturally existing molecules.

Few-photon multiple ionization of N2 by extreme ultraviolet free-electron laser radiation.

Few-photon multiple ionization of N2 was studied differentially in a reaction microscope using 44 eV, approximately 25 fs, intense ( approximately 10(13) W/cm(2)) photon pulses from FLASH. Sequential ionization is observed to dominate. For various intermediate charge states N(2)(n+0 we find a considerable excess of photons absorbed compared to the minimum number that would energetically be required. Photoionization of aligned N(2)(n+) ions, produced by photon absorption in sequential steps, is explored and few-photon absorption pathways are traced by inspecting kinetic energy releases and fragment-ion angular distributions.

Photo- and auger-electron recoil induced dynamics of interatomic Coulombic decay.

At photon energies near the Ne K edge it is shown that for 1s ionization the Auger electron, and for 2s ionization the fast photoelectron, launch vibrational wave packets in a Ne dimer. These wave packets then decay by emission of a slow electron via interatomic Coulombic decay (ICD). The measured and computed ICD electron spectra are shown to be significantly modified by the recoil induced nuclear motion.

Recoil-ion momentum distributions for two-photon double ionization of He and Ne by 44 eV free-electron laser radiation.

Recoil-ion momentum distributions for two-photon double ionization of He and Ne (variant Planck's over omega=44 eV) have been recorded with a reaction microscope at FLASH (the free-electron laser at Hamburg) at an intensity of approximately 1 x 10(14) W/cm2 exploring the dynamics of the two fundamental two-photon-two-electron reaction pathways, namely, sequential and direct (or nonsequential) absorption of the photons. We find strong differences in the recoil-ion momentum patterns for the two mechanisms pointing to the significantly different two-electron emission dynamics and thus provide serious constraints for theoretical models.

Single photon-induced symmetry breaking of H2 dissociation.

H2, the smallest and most abundant molecule in the universe, has a perfectly symmetric ground state. What does it take to break this symmetry? We found that the inversion symmetry can be broken by absorption of a linearly polarized photon, which itself has inversion symmetry. In particular, the emission of a photoelectron with subsequent dissociation of the remaining H+2 fragment shows no symmetry with respect to the ionic H+ and neutral H atomic fragments. This lack of symmetry results from the entanglement between symmetric and antisymmetric H+2 states that is caused by autoionization. The mechanisms behind this symmetry breaking are general for all molecules.