Identification of a previously unobserved dissociative ionization pathway in time-resolved photospectroscopy of the deuterium molecule.

A femtosecond vacuum ultraviolet (VUV) pulse with high spectral resolution (<200 meV) is selected from the laser-driven high order harmonics. This ultrafast VUV pulse is synchronized with an infrared (IR) laser pulse to study dissociative ionization in deuterium molecules. At a VUV photon energy of 16.95 eV, a previously unobserved bond-breaking pathway is found in which the dissociation direction does not follow the IR polarization. We interpret it as corresponding to molecules predissociating into two separated atoms, one of which is photoionized by the following IR pulse. A time resolved study allows us to determine the lifetime of the intermediate predissociation process to be about 1 ps. Additionally, the dissociative ionization pathways show high sensitivity to the VUV photon energy. As the VUV photon energy is blueshifted to 17.45 eV, the more familiar bond-softening channel is opened to compete with the newly discovered pathway. The interpretation of different pathways is supported by the energy sharing between the electron and nuclei.

Coherent electronic wave packet motion in C(60) controlled by the waveform and polarization of few-cycle laser fields.

Strong laser fields can be used to trigger an ultrafast molecular response that involves electronic excitation and ionization dynamics. Here, we report on the experimental control of the spatial localization of the electronic excitation in the C_{60} fullerene exerted by an intense few-cycle (4 fs) pulse at 720 nm. The control is achieved by tailoring the carrier-envelope phase and the polarization of the laser pulse. We find that the maxima and minima of the photoemission-asymmetry parameter along the laser-polarization axis are synchronized with the localization of the coherent electronic wave packet at around the time of ionization.

Transition between mechanisms of laser-induced field-free molecular orientation.

The transition between two distinct mechanisms for the laser-induced field-free orientation of CO molecules is observed via measurements of orientation revival times and subsequent comparison to theoretical calculations. In the first mechanism, which we find responsible for the orientation of CO up to peak intensities of 8 × 10(13) W/cm(2), the molecules are impulsively oriented through the hyperpolarizability interaction. At higher intensities, asymmetric depletion through orientation-selective ionization is the dominant orienting mechanism. In addition to the clear identification of the two regimes of orientation, we propose that careful measurements of the onset of the orientation depletion mechanism as a function of the laser intensity will provide a relatively simple route to calibrating absolute rates of nonperturbative strong-field molecular ionization.

Attosecond pulse characterization.

In this work we propose a novel procedure for the characterization of attosecond pulses. The method relies on the conversion of the attosecond pulse into electron wave-packets through photoionization of atoms in the presence of a weak IR field. It allows for the unique determination of the spectral phase making up the pulses by accurately taking into account the atomic physics of the photoionization process. The phases are evaluated by optimizing the fit of a perturbation theory calculation to the experimental result. The method has been called iPROOF (improved Phase Retrieval by Omega Oscillation Filtering) as it bears a similarity to the PROOF technique [Chini et al. Opt. Express 18, 13006 (2010)]. The procedure has been demonstrated for the characterization of an attosecond pulse train composed of odd and even harmonics. We observe a large phase shift between consecutive odd and even harmonics. The resulting attosecond pulse train has a complex structure not resembling a single attosecond pulse once per IR period, which is the case for zero phase. Finally, the retrieval procedure can be applied to the characterization of single attosecond pulses as well.

Ejection of quasi-free-electron pairs from the helium-atom ground state by single-photon absorption.

We investigate the single-photon double ionization of helium at photon energies of 440 and 800 eV. We observe doubly charged ions with close to zero momentum corresponding to electrons emitted back to back with equal energy. These slow ions are the unique fingerprint of an elusive quasifree photon double ionization mechanism predicted by Amusia et al. nearly four decades ago [J. Phys. B 8, 1248 (1975)]. It results from the nondipole part of the electromagnetic interaction. Our experimental data are supported by calculations performed using the convergent close-coupling and time-dependent close-coupling methods.

Attosecond control of orbital parity mix interferences and the relative phase of even and odd harmonics in an attosecond pulse train.

We experimentally demonstrate that atomic orbital parity mix interferences can be temporally controlled on an attosecond time scale. Electron wave packets are formed by ionizing argon gas with a comb of odd and even high-order harmonics, in the presence of a weak infrared field. Consequently, a mix of energy-degenerate even and odd parity states is fed in the continuum by one- and two-photon transitions. These interfere, leading to an asymmetric electron emission along the polarization vector. The direction of the emission can be controlled by varying the time delay between the comb and infrared field pulses. We show that such asymmetric emission provides information on the relative phase of consecutive odd and even order harmonics in the attosecond pulse train.

Control of electron localization in deuterium molecular ions using an attosecond pulse train and a many-cycle infrared pulse.

We demonstrate an experimental control of electron localization in deuterium molecular ions created and dissociated by the combined action of an attosecond pulse train and a many-cycle infrared (IR) pulse. The attosecond pulse train is synthesized using both even and odd high order harmonics of the driving IR frequency so that it can strobe the IR field once per IR cycle. An asymmetric ejection of the deuterium ions oscillates with the full IR period when the APT-IR time-delay is scanned. The observed control is due to the creation of a coherent superposition of 1s sigma{g} and 2p sigma{u} states via interference between one-photon and two-photon dissociation channels.

Complete photo-fragmentation of the deuterium molecule.

All properties of molecules--from binding and excitation energies to their geometry--are determined by the highly correlated initial-state wavefunction of the electrons and nuclei. Details of these correlations can be revealed by studying the break-up of these systems into their constituents. The fragmentation might be initiated by the absorption of a single photon, by collision with a charged particle or by exposure to a strong laser pulse: if the interaction causing the excitation is sufficiently understood, the fragmentation process can then be used as a tool to investigate the bound initial state. The interaction and resulting fragment motions therefore pose formidable challenges to quantum theory. Here we report the coincident measurement of the momenta of both nuclei and both electrons from the single-photon-induced fragmentation of the deuterium molecule. The results reveal that the correlated motion of the electrons is strongly dependent on the inter-nuclear separation in the molecular ground state at the instant of photon absorption.

Ion-energy dependence of asymmetric dissociation of D2 by a two-color laser field.

Two-color (800 and 400 nm) short (45 fs) linearly polarized pulses are used to ionize and dissociate D2 into a neutral deuterium atom and a deuteron. The yields and energies of the ions are measured left and right along the polarization vector. As the relative phase of the two colors is varied, strong yield asymmetries are found in the ion-energy regions traditionally identified as bond softening, above-threshold dissociation and rescattering. The asymmetries in these regions are quite different. A model based on the dynamic coupling by the laser field of the gerade and ungerade states in the molecular ion accounts for many of the observed features.

Field-free orientation of CO molecules by femtosecond two-color laser fields.

We report the first experimental observation of nonadiabatic field-free orientation of a heteronuclear diatomic molecule (CO) induced by an intense two-color (800 and 400 nm) femtosecond laser field. We monitor orientation by measuring fragment ion angular distributions after Coulomb explosion with an 800 nm pulse. The orientation of the molecules is controlled by the relative phase of the two-color field. The results are compared to quantum mechanical rigid rotor calculations. The demonstrated method can be applied to study molecular frame dynamics under field-free conditions in conjunction with a variety of spectroscopy methods, such as high-harmonic generation, electron diffraction, and molecular frame photoelectron emission.

Time-resolved momentum imaging system for molecular dynamics studies using a tabletop ultrafast extreme-ultraviolet light source.

We describe a momentum imaging setup for direct time-resolved studies of ionization-induced molecular dynamics. This system uses a tabletop ultrafast extreme-ultraviolet (EUV) light source based on high harmonic upconversion of a femtosecond laser. The high photon energy (around 42 eV) allows access to inner-valence states of a variety of small molecules via single photon excitation, while the sub--10-fs pulse duration makes it possible to follow the resulting dynamics in real time. To obtain a complete picture of molecular dynamics following EUV induced photofragmentation, we apply the versatile cold target recoil ion momentum spectroscopy reaction microscope technique, which makes use of coincident three-dimensional momentum imaging of fragments resulting from photoexcitation. This system is capable of pump-probe spectroscopy by using a combination of EUV and IR laser pulses with either beam as a pump or probe pulse. We report several experiments performed using this system.

Precision control of carrier-envelope phase in grating based chirped pulse amplifiers.

It is demonstrated that the carrier-envelope (CE) phase of pulses from a high power ultrafast laser system with a grating-based stretcher and compressor can be stabilized to a root mean square (rms) value of 180 mrad over almost 2 hours, excluding a brief re-locking period. The stabilization was accomplished via feedback control of the grating separation in the stretcher. It shows that the long term CE phase stability of a grating based chirped pulse amplification system can be as good as that of lasers using a glass-block stretcher and a prism pair compressor. Moreover, by adjusting the grating separation to preset values, the relative CE phase could be locked to an arbitrary value in the range of 2pi. This method is better than using a pair of wedge plates to adjust the phase after the hollow-core fiber compressor. The CE phase stabilization after a hollow-core fiber compressor was confirmed by a CE-phase meter based on the measurement of the left-to-right asymmetry of electrons produced by above-threshold ionization.

Transition from SAMO to Rydberg State Ionization in C60 in Femtosecond Laser Fields.

The transition between two distinct ionization mechanisms in femtosecond laser fields at 785 nm is observed for C60 molecules. The transition occurs in the investigated intensity range from 3 to 20 TW/cm2 and is visualized in electron kinetic energy spectra below the one-photon energy (1.5 eV) obtained via velocity map imaging. Assignment of several observed broad spectral peaks to ionization from superatom molecular orbitals (SAMOs) and Rydberg states is based on time-dependent density functional theory simulations. We find that ionization from SAMOs dominates the spectra for intensities below 5 TW/cm2. As the intensity increases, Rydberg state ionization exceeds the prominence of SAMOs. Using short laser pulses (20 fs) allowed uncovering of distinct six-lobe photoelectron angular distributions with kinetic energies just above the threshold (below 0.2 eV), which we interpret as over-the-barrier ionization of shallow f-Rydberg states in C60.

Atomic dynamics in single and multi-photon double ionization: An experimental comparison.

We have used a multi-particle imaging technique (COLTRIMS) to observe the double ionization of rare gas atoms by multi-photon absorption of 800 nm (1.5 eV) femto-second laser pulses and by single photon absorption (synchrotron radiation). Both processes are mediated by electron correlation. We discuss similarities and differences in the three-body final state momentum distributions.

Angular correlation between photoelectrons and auger electrons from K-shell ionization of neon.

We have used cold target recoil ion momentum spectroscopy to study the continuum correlation between the photoelectron of core-photoionized neon and the subsequent Auger electron. We observe a strong angular correlation between the two electrons. Classical trajectory Monte Carlo calculations agree quite well with the photoelectron energy distribution that is shifted due to the potential change associated with Auger decay. However, a striking discrepancy results in the distribution of the relative angle between Auger and photoelectron. The classical model predicts a shift in photoelectron flux away from the Auger emission direction, and the data strikingly reveal that the flux is lost rather than diverted, indicating that the two-step interpretation of photoionization followed by Auger emission is insufficient to fully describe the core-photoionization process.

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.

Evidence of wave-particle duality for single fast hydrogen atoms.

We report the direct observation of interference effects in a Young's double-slit experiment where the interfering waves are two spatially separated components of the de Broglie wave of single 1.3 MeV hydrogen atoms formed close to either target nucleus in H++H2 electron-transfer collisions. Quantum interference strongly influences the results even though the hydrogen atoms have a de Broglie wavelength, lambda_{dB}, as small as 25 fm.

Large-angle electron diffraction structure in laser-induced rescattering from rare gases.

We have measured full momentum images of electrons rescattered from Xe, Kr, and Ar following the liberation of the electrons from these atoms by short, intense laser pulses. At high momenta the spectra show angular structure (diffraction) which is very target dependent and in good agreement with calculated differential cross sections for the scattering of free electrons from the corresponding ionic cores.

Ultrafast probing of core hole localization in N2.

Although valence electrons are clearly delocalized in molecular bonding frameworks, chemists and physicists have long debated the question of whether the core vacancy created in a homonuclear diatomic molecule by absorption of a single x-ray photon is localized on one atom or delocalized over both. We have been able to clarify this question with an experiment that uses Auger electron angular emission patterns from molecular nitrogen after inner-shell ionization as an ultrafast probe of hole localization. The experiment, along with the accompanying theory, shows that observation of symmetry breaking (localization) or preservation (delocalization) depends on how the quantum entangled Bell state created by Auger decay is detected by the measurement.

Interference in the collective electron momentum in double photoionization of H2.

We investigate single-photon double ionization of H(2) by 130 to 240 eV circularly polarized photons. We find a double slitlike interference pattern in the sum momentum of both electrons in the molecular frame which survives integration over all other degrees of freedom. The difference momentum and the individual electron momentum distributions do not show such a robust interference pattern. We show that this interference results from a non-Heitler-London fraction of the H(2) ground state where both electrons are at the same atomic center.