Intermolecular interactions probed by rotational dynamics in gas-phase clusters.

The rotational dynamics of a molecule is sensitive to neighboring atoms or molecules, which can be used to probe the intermolecular interactions in the gas phase. Here, we real-time track the laser-driven rotational dynamics of a single N2 molecule affected by neighboring Ar atoms using coincident Coulomb explosion imaging. We find that the alignment trace of N-N axis decays fast and only persists for a few picoseconds when an Ar atom is nearby. We show that the decay rate depends on the rotational geometry of whether the Ar atom stays in or out of the rotational plane of the N2 molecule. Additionally, the vibration of the van der Waals bond is found to be excited through coupling with the rotational N-N axis. The observations are well reproduced by solving the time-dependent Schrödinger equation after taking the interaction potential between the N2 and Ar into consideration. Our results demonstrate that environmental effects on a molecular level can be probed by directly visualizing the rotational dynamics.

Ultrafast Kapitza-Dirac effect.

Similar to the optical diffraction of light passing through a material grating, the Kapitza-Dirac effect occurs when an electron is diffracted by a standing light wave. In its original description, the effect is time independent. Here, we extended the Kapitza-Dirac effect to the time domain. By tracking the spatiotemporal evolution of a pulsed electron wave packet diffracted by a 60-femtosecond (where one femtosecond = 10-15 seconds) standing wave pulse in a pump-probe scheme, we observed time-dependent diffraction patterns. The fringe spacing in the observed pattern differs from that generated by the conventional Kapitza-Dirac effect. By exploiting this time-resolved diffraction scheme, we can access the time evolution of the phase properties of a free electron and potentially image ionic potentials and electronic decoherences.

Interatomic Coulombic decay in small helium clusters.

Interatomic Coulombic decay (ICD) is an ultrafast non-radiative electronic decay process wherein an excited atom transfers its excess energy to a neighboring species leading to the ionization of the latter. In helium clusters, ICD can take place, for example, after simultaneous ionization and excitation of one helium atom within the cluster. After ICD, two helium ions are created and the system undergoes a Coulomb explosion. In this work, we investigate theoretically ICD in small helium clusters containing between two and seven atoms and compare our findings to two sets of coincidence measurements on clusters of different mean sizes. We provide a prediction on the lifetime of the excited dimer and show that ICD is faster for larger clusters. This is due to (i) the increased number of neighboring atoms (and therefore the number of decay channels) and (ii) the substantial decrease of the interatomic distances. In order to provide more details on the decay dynamics, we report on the kinetic-energy distributions of the helium ions. These distributions clearly show that the ions may undergo charge exchange with the neutral atoms within the cluster, such process is known as frustrated Coulomb explosion. The probability for these charge-exchange processes increases with the size of the clusters and is reflected in our calculated and measured kinetic-energy distributions. These distributions are therefore characteristics of the size distribution of small helium clusters.

Ultrafast formation dynamics of D3+ from the light-driven bimolecular reaction of the D2-D2 dimer.

The light-driven formation of trihydrogen cation has been attracting considerable attention because of its important role as an initiator of chemical reactions in interstellar clouds. To understand the formation dynamics, most previous studies focused on creating H3+ or D3+ from unimolecular reactions of various organic molecules. Here we observe and characterize the ultrafast formation dynamics of D3+ from a bimolecular reaction, using pump-probe experiments that employ ultrashort laser pulses to probe its formation from a D2-D2 dimer. Our molecular dynamics simulations provide an intuitive representation of the reaction dynamics, which agree well with the experimental observation. We also show that the emission direction of D3+ can be controlled using a tailored two-colour femtosecond laser field. The underlying control mechanism is in line with what is known from the light control of electron localization in the bond breaking of single molecules.

Alternative Pathway to Double-Core-Hole States.

Excited double-core-hole states of isolated water molecules resulting from the sequential absorption of two x-ray photons have been investigated. These states are formed through an alternative pathway, where the initial step of core ionization is accompanied by the shake-up of a valence electron, leading to the same final states as in the core-ionization followed by core-excitation pathway. The capability of the x-ray free-electron laser to deliver very intense, very short, and tunable light pulses is fully exploited to identify the two different pathways.

A new route for enantio-sensitive structure determination by photoelectron scattering on molecules in the gas phase.

X-Ray as well as electron diffraction are powerful tools for structure determination of molecules. Studies on randomly oriented molecules in the gas phase address cases in which molecular crystals cannot be generated or the interaction-free molecular structure is to be addressed. Such studies usually yield partial geometrical information, such as interatomic distances. Here, we present a complementary approach, which allows obtaining insight into the structure, handedness, and even detailed geometrical features of molecules in the gas phase. Our approach combines Coulomb explosion imaging, the information that is encoded in the molecular-frame diffraction pattern of core-shell photoelectrons and ab initio computations. Using a loop-like analysis scheme, we are able to deduce specific molecular coordinates with sensitivity even to the handedness of chiral molecules and the positions of individual atoms, e.g., protons.

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.

Influence of the emission site on the photoelectron circular dichroism in trifluoromethyloxirane.

We report a joint experimental and theoretical study of the differential photoelectron circular dichroism (PECD) in inner-shell photoionization of uniaxially oriented trifluoromethyloxirane. By adjusting the photon energy of the circularly polarized synchrotron radiation, we address 1s-photoionization of the oxygen, different carbon, and all fluorine atoms. The photon energies were chosen such that in all cases electrons with a similar kinetic energy of about 11 eV are emitted. Employing coincident detection of electrons and fragment ions, we concentrate on identical molecular fragmentation channels for all of the electron-emitter scenarios. Thereby, we systematically examine the influence of the emission site of the photoelectron wave on the differential PECD. We observe large differences in the PECD signals. The present experimental results are supported by corresponding relaxed-core Hartree-Fock calculations.

Magnetic-Field Effect as a Tool to Investigate Electron Correlation in Strong-Field Ionization.

The influence of the magnetic component of the driving electromagnetic field is often neglected when investigating light-matter interaction. We show that the magnetic component of the light field plays an important role in nonsequential double ionization, which serves as a powerful tool to investigate electron correlation. We investigate the magnetic-field effects in double ionization of xenon atoms driven by near-infrared ultrashort femtosecond laser pulses and find that the mean forward shift of the electron momentum distribution in light-propagation direction agrees well with the classical prediction, where no under-barrier or recollisional nondipole enhancement is observed. By extending classical trajectory Monte Carlo simulations beyond the dipole approximation, we reveal that double ionization proceeds via recollision-induced doubly excited states, followed by subsequent sequential over-barrier field ionization of the two electrons. In agreement with this model, the binding energies do not lead to an additional nondipole forward shift of the electrons. Our findings provide a new method to study electron correlation by exploiting the effect of the magnetic component of the electromagnetic field.

Photoelectron energy peaks shift against the radiation pressure in strong-field ionization.

The photoelectric effect describes the ejection of an electron upon absorption of one or several photons. The kinetic energy of this electron is determined by the photon energy reduced by the binding energy of the electron and, if strong laser fields are involved, by the ponderomotive potential in addition. It has therefore been widely taken for granted that for atoms and molecules, the photoelectron energy does not depend on the electron's emission direction, but theoretical studies have questioned this since 1990. Here, we provide experimental evidence that the energies of photoelectrons emitted against the light propagation direction are shifted toward higher values, while those electrons that are emitted along the light propagation direction are shifted to lower values. We attribute the energy shift to a nondipole contribution to the ponderomotive potential that is due to the interaction of the moving electrons with the incident photons.

Magnetic-Field Effect in High-Order Above-Threshold Ionization.

We experimentally and theoretically investigate the influence of the magnetic component of an electromagnetic field on high-order above-threshold ionization of xenon atoms driven by ultrashort femtosecond laser pulses. The nondipole shift of the electron momentum distribution along the light-propagation direction for high energy electrons beyond the 2U_{p} classical cutoff is found to be vastly different from that below this cutoff, where U_{p} is the ponderomotive potential of the driving laser field. A local minimum structure in the momentum dependence of the nondipole shift above the cutoff is identified for the first time. With the help of classical and quantum-orbit analysis, we show that large-angle rescattering of the electrons strongly alters the partitioning of the photon momentum between electron and ion. The sensitivity of the observed nondipole shift to the electronic structure of the target atom is confirmed by three-dimensional time-dependent Schrödinger equation simulations for different model potentials. Our work paves the way toward understanding the physics of extreme light-matter interactions at long wavelengths and high electron kinetic energies.

Measuring the photoelectron emission delay in the molecular frame.

How long does it take to emit an electron from an atom? This question has intrigued scientists for decades. As such emission times are in the attosecond regime, the advent of attosecond metrology using ultrashort and intense lasers has re-triggered strong interest on the topic from an experimental standpoint. Here, we present an approach to measure such emission delays, which does not require attosecond light pulses, and works without the presence of superimposed infrared laser fields. We instead extract the emission delay from the interference pattern generated as the emitted photoelectron is diffracted by the parent ion's potential. Targeting core electrons in CO, we measured a 2d map of photoelectron emission delays in the molecular frame over a wide range of electron energies. The emission times depend drastically on the photoelectrons' emission directions in the molecular frame and exhibit characteristic changes along the shape resonance of the molecule.

Photoelectron circular dichroism of O 1s-photoelectrons of uniaxially oriented trifluoromethyloxirane: energy dependence and sensitivity to molecular configuration.

The photoelectron circular dichroism (PECD) of the O 1s-photoelectrons of trifluoromethyloxirane (TFMOx) is studied experimentally and theoretically for different photoelectron kinetic energies. The experiments were performed employing circularly polarized synchrotron radiation and coincident electron and fragment ion detection using cold target recoil ion momentum spectroscopy. The corresponding calculations were performed by means of the single center method within the relaxed-core Hartree-Fock approximation. We concentrate on the energy dependence of the differential PECD of uniaxially oriented TFMOx molecules, which is accessible through the employed coincident detection. We also compare the results for the differential PECD of TFMOx to those obtained for the equivalent fragmentation channel and similar photoelectron kinetic energy of methyloxirane (MOx), studied in our previous work. Thereby, we investigate the influence of the substitution of the methyl group by the trifluoromethyl group at the chiral center on the molecular chiral response. Finally, the presently obtained angular distribution parameters are compared to those available in the literature.

Double Core-Hole Generation in O_{2} Molecules Using an X-Ray Free-Electron Laser: Molecular-Frame Photoelectron Angular Distributions.

We report on a multiparticle coincidence experiment performed at the European X-ray Free-Electron Laser at the Small Quantum Systems instrument using a COLTRIMS reaction microscope. By measuring two ions and two electrons in coincidence, we investigate double core-hole generation in O_{2} molecules in the gas phase. Single-site and two-site double core holes have been identified and their molecular-frame electron angular distributions have been obtained for a breakup of the oxygen molecule into two doubly charged ions. The measured distributions are compared to results of calculations performed within the frozen- and relaxed-core Hartree-Fock approximations.

Interatomic and Intermolecular Coulombic Decay.

Interatomic or intermolecular Coulombic decay (ICD) is a nonlocal electronic decay mechanism occurring in weakly bound matter. In an ICD process, energy released by electronic relaxation of an excited atom or molecule leads to ionization of a neighboring one via Coulombic electron interactions. ICD has been predicted theoretically in the mid nineties of the last century, and its existence has been confirmed experimentally approximately ten years later. Since then, a number of fundamental and applied aspects have been studied in this quickly growing field of research. This review provides an introduction to ICD and draws the connection to related energy transfer and ionization processes. The theoretical approaches for the description of ICD as well as the experimental techniques developed and employed for its investigation are described. The existing body of literature on experimental and theoretical studies of ICD processes in different atomic and molecular systems is reviewed.

Zeptosecond birth time delay in molecular photoionization.

Photoionization is one of the fundamental light-matter interaction processes in which the absorption of a photon launches the escape of an electron. The time scale of this process poses many open questions. Experiments have found time delays in the attosecond (10-18 seconds) domain between electron ejection from different orbitals, from different electronic bands, or in different directions. Here, we demonstrate that, across a molecular orbital, the electron is not launched at the same time. Rather, the birth time depends on the travel time of the photon across the molecule, which is 247 zeptoseconds (1 zeptosecond = 10-21 seconds) for the average bond length of molecular hydrogen. Using an electron interferometric technique, we resolve this birth time delay between electron emission from the two centers of the hydrogen molecule.

Observation of Photoion Backward Emission in Photoionization of He and N_{2}.

We experimentally investigate the effects of the linear photon momentum on the momentum distributions of photoions and photoelectrons generated in one-photon ionization in an energy range of 300 eV≤E_{γ}≤40 keV. Our results show that for each ionization event the photon momentum is imparted onto the photoion, which is essentially the system's center of mass. Nevertheless, the mean value of the ion momentum distribution along the light propagation direction is backward-directed by -3/5 times the photon momentum. These results experimentally confirm a 90-year-old prediction.

Visualizing the Geometry of Hydrogen Dimers.

The simplest molecular dimer, H2-H2, poses a challenge to both experiment and theory as a system with a multidimensional energy surface that supports only a single weakly bound quantum state. Here, we provide a direct experimental image of the structure of hydrogen dimers [(H2)2, H2-D2, and (D2)2] obtained via femtosecond laser-induced Coulomb explosion imaging. Our results indicate that hydrogen dimers are not restricted to a particular geometry but rather occur as a mixture of all possible configurations. The measured intermolecular distance distributions were used to deduce the isotropic intermolecular potential as well as the binding energies of the dimers.

Link between Photoelectron Circular Dichroism and Fragmentation Channel in Strong Field Ionization.

The investigation of the photoelectron circular dichroism (PECD) in the strong field regime (800 nm, 6.9 × 1013 W/cm2) on methyloxirane (MOX) reveals a flip of the sign of PECD between different fragmentation channels. This finding is of great importance for future experiments and applications in chemistry or pharmacy using PECD in the strong field regime as analysis method. We suggest that the observed sign change of PECD is not caused by ionization from different orbitals but by effectively selecting differently oriented nonisotropic subsamples of molecules via the fragmentation channel.

Double-slit photoelectron interference in strong-field ionization of the neon dimer.

Wave-particle duality is an inherent peculiarity of the quantum world. The double-slit experiment has been frequently used for understanding different aspects of this fundamental concept. The occurrence of interference rests on the lack of which-way information and on the absence of decoherence mechanisms, which could scramble the wave fronts. Here, we report on the observation of two-center interference in the molecular-frame photoelectron momentum distribution upon ionization of the neon dimer by a strong laser field. Postselection of ions, which are measured in coincidence with electrons, allows choosing the symmetry of the residual ion, leading to observation of both, gerade and ungerade, types of interference.