ABSTRACT
We report the first systematic photoelectron measurements of the three outer-valence bands of liquid water as a function of the ionizing photon energy in the near-threshold region. We use extreme-ultraviolet (XUV) radiation tunable between â¼17.1 and 35.6 eV, obtained through monochromatization of a high-harmonic source. We show that the absolute values of the apparent vertical ionization energies and their respective peak widths show a decreasing trend of their magnitudes with increasing photon energy close to the ionization threshold. We find that the observed effects do not only depend on the electron kinetic energy but are also different for the various outer-valence bands. These observations are consistent with, but not fully explained by, the effects of inelastic electron scattering.
ABSTRACT
Electronic dynamics in liquids are of fundamental importance, but time-resolved experiments have so far remained limited to the femtosecond time scale. We report the extension of attosecond spectroscopy to the liquid phase. We measured time delays of 50 to 70 attoseconds between the photoemission from liquid water and that from gaseous water at photon energies of 21.7 to 31.0 electron volts. These photoemission delays can be decomposed into a photoionization delay sensitive to the local environment and a delay originating from electron transport. In our experiments, the latter contribution is shown to be negligible. By referencing liquid water to gaseous water, we isolated the effect of solvation on the attosecond photoionization dynamics of water molecules. Our methods define an approach to separating bound and unbound electron dynamics from the structural response of the solvent.
ABSTRACT
High intensity XUV radiation from a free-electron laser (FEL) was used to create a nanoplasma inside ammonia clusters with the intent of studying the resulting electron-ion interactions and their interplay with plasma evolution. In a plasma-like state, electrons with kinetic energy lower than the local collective Coulomb potential of the positive ionic core are trapped in the cluster and take part in secondary processes (e.g. electron-impact excitation/ionization and electron-ion recombination) which lead to subsequent excited and neutral molecular fragmentation. Using a time-delayed UV laser, the dynamics of the excited atomic and molecular states are probed from -0.1 ps to 18 ps. We identify three different phases of molecular fragmentation that are clearly distinguished by the effect of the probe laser on the ionic and electronic yield. We propose a simple model to rationalize our data and further identify two separate channels leading to the formation of excited hydrogen.
ABSTRACT
The ionization energy of liquid water is one of its most fundamental properties, an important benchmark for first-principles electronic-structure calculations and a crucial reference in the growing field of liquid-phase photoelectron spectroscopy. Despite this significance, a consensus on its value appears to be missing in the literature. Therefore, we use a monochromatized high-harmonic light source to perform detailed measurements of the ionization energy of liquid water in the presence of a tunable bias voltage applied to the liquid jet. Our results suggest that this simple method is sufficient to simultaneously compensate the effects of the streaming potential and that of the vacuum-level offset between the liquid and the photoelectron spectrometer. Our measurements yield corrected values of the vertical and adiabatic ionization energies of the 1b1 band of bulk liquid water of 11.67(15) and 10.12(15) eV, respectively. Our method is broadly applicable and is likely to result in corrections to the measured ionization energies of solvated species as well.
ABSTRACT
We present calculations of time-dependent photoelectron spectra of NO2 after excitation to the A-band for comparison with extreme-ultraviolet (XUV) time-resolved photoelectron spectroscopy. We employ newly calculated potential energy surfaces of the two lowest-lying coupled 2A' states obtained from multi-reference configuration-interaction calculations to propagate the photo-excited wave packet using a split-step-operator method. The propagation includes the nonadiabatic coupling of the potential surfaces as well as the explicit interaction with the pump pulse centered at 3.1 eV (400 nm). A semiclassical approach to calculate the time-dependent photoelectron spectrum arising from the ionization to the eight energetically lowest-lying states of the cation allows us to reproduce the static experimental spectrum up to a binding energy of 16 eV and enables direct comparisons with XUV time-resolved photoelectron spectroscopy.
ABSTRACT
Strong-field photoelectron holography and laser-induced electron diffraction (LIED) are two powerful emerging methods for probing the ultrafast dynamics of molecules. However, both of them have remained restricted to static systems and to nuclear dynamics induced by strong-field ionization. Here we extend these promising methods to image purely electronic valence-shell dynamics in molecules using photoelectron holography. In the same experiment, we use LIED and photoelectron holography simultaneously, to observe coupled electronic-rotational dynamics taking place on similar timescales. These results offer perspectives for imaging ultrafast dynamics of molecules on femtosecond to attosecond timescales.
ABSTRACT
Time-resolved x-ray absorption spectroscopy (TR-XAS) has so far practically been limited to large-scale facilities, to subpicosecond temporal resolution, and to the condensed phase. We report the realization of TR-XAS with a temporal resolution in the low femtosecond range by developing a tabletop high-harmonic source reaching up to 350 electron volts, thus partially covering the spectral region of 280 to 530 electron volts, where water is transmissive. We used this source to follow previously unexamined light-induced chemical reactions in the lowest electronic states of isolated CF4+ and SF6+ molecules in the gas phase. By probing element-specific core-to-valence transitions at the carbon K-edge or the sulfur L-edges, we characterized their reaction paths and observed the effect of symmetry breaking through the splitting of absorption bands and Rydberg-valence mixing induced by the geometry changes.
ABSTRACT
We report measurements of energy-dependent photoionization delays between the two outermost valence shells of N_{2}O and H_{2}O. The combination of single-shot signal referencing with the use of different metal foils to filter the attosecond pulse train enables us to extract delays from congested spectra. Remarkably large delays up to 160 as are observed in N_{2}O, whereas the delays in H_{2}O are all smaller than 50 as in the photon-energy range of 20-40 eV. These results are interpreted by developing a theory of molecular photoionization delays. The long delays measured in N_{2}O are shown to reflect the population of molecular shape resonances that trap the photoelectron for a duration of up to â¼110 as. The unstructured continua of H_{2}O result in much smaller delays at the same photon energies. Our experimental and theoretical methods make the study of molecular attosecond photoionization dynamics accessible.
ABSTRACT
Monochromatization of high-harmonic sources has opened fascinating perspectives regarding time-resolved photoemission from all phases of matter. Such studies have invariably involved the use of spectral filters or spectrally dispersive optical components that are inherently lossy and technically complex. Here we present a new technique for the spectral selection of near-threshold harmonics and their spatial separation from the driving beams without any optical elements. We discover the existence of a narrow phase-matching gate resulting from the combination of the non-collinear generation geometry in an extended medium, atomic resonances and absorption. Our technique offers a filter contrast of up to 104 for the selected harmonics against the adjacent ones and offers multiple temporally synchronized beamlets in a single unified scheme. We demonstrate the selective generation of 133, 80 or 56 nm femtosecond pulses from a 400-nm driver, which is specific to the target gas. These results open new pathways towards phase-sensitive multi-pulse spectroscopy in the vacuum- and extreme-ultraviolet, and frequency-selective output coupling from enhancement cavities.
ABSTRACT
We report angle- and momentum-resolved measurements of the dissociative ionization and Coulomb explosion of methyl halides (CH3F, CH3Cl, CH3Br, and CH3I) in intense phase-controlled two-color laser fields. At moderate laser intensities, we find that the emission asymmetry of low-energy CH3(+) fragments from the CH3(+) + X(+) (X = F, Cl, Br, or I) channel reflects the asymmetry of the highest occupied molecular orbital of the neutral molecule with important contributions from the Stark effect. This asymmetry is correctly predicted by the weak-field asymptotic theory, provided that the Stark effect on the ionization potentials is calculated using a nonperturbative multielectron approach. In the case of high laser intensities, we observe a reversal of the emission asymmetries for high-energy CH3(+) fragments, originating from the dissociation of CH3X(q+) with q ≥ 2. We propose ionization to electronically excited states to be at the origin of the reversed asymmetries. We also report the measurements of the emission asymmetry of H3(+), which is found to be identical to that of the low-energy CH3(+) fragments measured at moderate laser intensities. All observed fragmentation channels are assigned with the help of CCSD(T) calculations. Our results provide a benchmark for theories of strong-field processes and demonstrate the importance of multielectron effects in new aspects of the molecular response to intense laser fields.
