XUV-Initiated Dissociation Dynamics of Molecular Oxygen (O2).

We performed a time-resolved spectroscopy experiment on the dissociation of oxygen molecules after the interaction with intense extreme-ultraviolet (XUV) light from the free-electron laser in Hamburg at Deutsches Elektronen-Synchrotron. Using an XUV-pump/XUV-probe transient-absorption geometry with a split-and-delay unit, we observe the onset of electronic transitions in the O2+ cation near 50 eV photon energy, marking the end of the progression from a molecule to two isolated atoms. We observe two different time scales of 290 ± 53 and 180 ± 76 fs for the emergence of different ionic transitions, indicating different dissociation pathways taken by the departing oxygen atoms. With regard to the emerging opportunities of tuning the central frequencies of pump and probe pulses and of increasing the probe-pulse bandwidth, future pump-probe transient-absorption experiments are expected to provide a detailed view of the coupled nuclear and electronic dynamics during molecular dissociation.

Distinction of Electron Dispersion in Time-Resolved Photoemission Spectroscopy.

While recent experiments provided compelling evidence for an intricate dependence of attosecond photoemission-time delays on the solid's electronic band structure, the extent to which electronic transport and dispersion in solids can be imaged in time-resolved photoelectron (PE) spectra remains poorly understood. Emphasizing the distinction between photoemission time delays measured with two-photon, two-color interferometric spectroscopy, and transport times, we demonstrate how the effect of energy dispersion in the solid on photoemission delays can, in principle, be observed in interferometric photoemission. We reveal analytically a scaling relation between the PE transport time in the solid and the observable photoemission delay and confirm this relation in numerical simulations for a model system. We trace photoemission delays to the phase difference the PE accumulates inside the solid and, in particular, predict negative photoemission delays. Based on these findings, we suggest a novel time-domain interferometric solid-state energy-momentum-dispersion imaging method.

Distinguishing attosecond electron-electron scattering and screening in transition metals.

Electron-electron interactions are the fastest processes in materials, occurring on femtosecond to attosecond timescales, depending on the electronic band structure of the material and the excitation energy. Such interactions can play a dominant role in light-induced processes such as nano-enhanced plasmonics and catalysis, light harvesting, or phase transitions. However, to date it has not been possible to experimentally distinguish fundamental electron interactions such as scattering and screening. Here, we use sequences of attosecond pulses to directly measure electron-electron interactions in different bands of different materials with both simple and complex Fermi surfaces. By extracting the time delays associated with photoemission we show that the lifetime of photoelectrons from the d band of Cu are longer by ∼100 as compared with those from the same band of Ni. We attribute this to the enhanced electron-electron scattering in the unfilled d band of Ni. Using theoretical modeling, we can extract the contributions of electron-electron scattering and screening in different bands of different materials with both simple and complex Fermi surfaces. Our results also show that screening influences high-energy photoelectrons (≈20 eV) significantly less than low-energy photoelectrons. As a result, high-energy photoelectrons can serve as a direct probe of spin-dependent electron-electron scattering by neglecting screening. This can then be applied to quantifying the contribution of electron interactions and screening to low-energy excitations near the Fermi level. The information derived here provides valuable and unique information for a host of quantum materials.

Imaging Plasmonic Fields with Atomic Spatiotemporal Resolution.

We propose a scheme for the reconstruction of plasmonic near fields at isolated nanoparticles from infrared-streaked extreme-ultraviolet photoemission spectra. Based on quantum-mechanically modeled spectra, we demonstrate and analyze the accurate imaging of the IR-streaking-pulse-induced transient plasmonic fields at the surface of gold nanospheres and nanoshells with subfemtosecond temporal and subnanometer spatial resolution.

Criterion for Distinguishing Sequential from Nonsequential Contributions to the Double Ionization of Helium in Ultrashort Extreme-Ultraviolet Pulses.

We quantify sequential and nonsequential contributions in two-photon double ionization of helium atoms by intense ultrashort extreme-ultraviolet pulses with central photon energies ℏω_{ctr} near the sequential double-ionization threshold. If the spectrum of such pulses overlaps both the sequential (ℏω>54.4 eV) and nonsequential (ℏω<54.4 eV) double-ionization regimes, the sequential and nonsequential double-ionization mechanisms are difficult to distinguish. By tracking the double-ionization asymmetry in joint photoelectron angular distributions, we introduce the two-electron forward-backward-emission asymmetry as a measure that allows the distinction of sequential and nonsequential contributions. Specifically, for ℏω_{ctr}=50 eV pulses with a sine-squared temporal profile, we find that the sequential double-ionization contribution is the largest at a pulse length of 650 as, due to competing temporal and spectral constraints. In addition, we validate a simple heuristic expression for the sequential double-ionization contribution in comparison with ab initio calculations.

Time-resolving state-specific molecular dissociation with XUV broadband absorption spectroscopy.

The electronic and nuclear dynamics inside molecules are essential for chemical reactions, where different pathways typically unfold on ultrafast timescales. Extreme ultraviolet (XUV) light pulses generated by free-electron lasers (FELs) allow atomic-site and electronic-state selectivity, triggering specific molecular dynamics while providing femtosecond resolution. Yet, time-resolved experiments are either blind to neutral fragments or limited by the spectral bandwidth of FEL pulses. Here, we combine a broadband XUV probe pulse from high-order harmonic generation with an FEL pump pulse to observe dissociation pathways leading to fragments in different quantum states. We temporally resolve the dissociation of a specific O2+ state into two competing channels by measuring the resonances of ionic and neutral fragments. This scheme can be applied to investigate convoluted dynamics in larger molecules relevant to diverse science fields.

Attosecond time-resolved autoionization of argon.

Autoionization of argon atoms was studied experimentally by transient absorption spectroscopy with isolated attosecond pulses. The peak position, intensity, linewidth, and shape of the 3s3p6np ¹P Fano resonance series (26.6-29.2 eV) were modified by intense few-cycle near infrared laser pulses, while the delay between the attosecond pulse and the laser pulse was changed by a few femtoseconds. Numerical simulations revealed that the experimentally observed splitting of the 3s3p64p ¹P line is caused by the coupling between two short-lived highly excited states in the strong laser field.

Steering the electron in H2(+) by nuclear wave packet dynamics.

By combining carrier-envelope phase (CEP) stable light fields and the traditional method of optical pump-probe spectroscopy we study electron localization in dissociating H2(+) molecular ions. Localization and localizability of electrons is observed to strongly depend on the time delay between the two CEP-stable laser pulses with a characteristic periodicity corresponding to the oscillating molecular wave packet. Variation of the pump-probe delay time allows us to uncover the underlying physical mechanism for electron localization, which are two distinct sets of interfering dissociation channels that exhibit specific temporal signatures in their asymmetry response.

Electron localization in molecular fragmentation of H2 by carrier-envelope phase stabilized laser pulses.

Fully differential data for H2 dissociation in ultrashort (6 fs, 760 nm), linearly polarized, intense (0.44 PW/cm{2}) laser pulses with a stabilized carrier-envelope phase (CEP) were recorded with a reaction microscope. Depending on the CEP, the molecular orientation, and the kinetic energy release (KER), we find asymmetric proton emission at low KERs (0-3 eV), basically predicted by Roudnev and Esry, and much stronger than reported by Kling et al. Wave packet propagation calculations reproduce the salient features and discard, together with the observed KER-independent electron asymmetry, the first ionization step to be the reason for the asymmetric proton emission.

Strong-field modulated diffraction effects in the correlated electron-nuclear motion in dissociating H(2+).

We show that the electronic dynamics in a molecule driven by a strong field is complex and potentially even counterintuitive. As a prototype example, we simulate the interaction of a dissociating H2+ molecule with an intense infrared laser pulse. Depending on the laser intensity, the direction of the electron's motion between the two nuclei is found to follow or oppose the classical laser-electric force. We explain the sensitive dependence of the correlated electronic-nuclear motion in terms of the diffracting electronic momentum distribution of the dissociating two-center system. The distribution is dynamically modulated by the nuclear motion and periodically shifted in the oscillating infrared electric field.