Attosecond delays in X-ray molecular ionization.

The photoelectric effect is not truly instantaneous but exhibits attosecond delays that can reveal complex molecular dynamics1-7. Sub-femtosecond-duration light pulses provide the requisite tools to resolve the dynamics of photoionization8-12. Accordingly, the past decade has produced a large volume of work on photoionization delays following single-photon absorption of an extreme ultraviolet photon. However, the measurement of time-resolved core-level photoionization remained out of reach. The required X-ray photon energies needed for core-level photoionization were not available with attosecond tabletop sources. Here we report measurements of the X-ray photoemission delay of core-level electrons, with unexpectedly large delays, ranging up to 700 as in NO near the oxygen K-shell threshold. These measurements exploit attosecond soft X-ray pulses from a free-electron laser to scan across the entire region near the K-shell threshold. Furthermore, we find that the delay spectrum is richly modulated, suggesting several contributions, including transient trapping of the photoelectron owing to shape resonances, collisions with the Auger-Meitner electron that is emitted in the rapid non-radiative relaxation of the molecule and multi-electron scattering effects. The results demonstrate how X-ray attosecond experiments, supported by comprehensive theoretical modelling, can unravel the complex correlated dynamics of core-level photoionization.

The time-resolved atomic, molecular and optical science instrument at the Linac Coherent Light Source.

The newly constructed time-resolved atomic, molecular and optical science instrument (TMO) is configured to take full advantage of both linear accelerators at SLAC National Accelerator Laboratory, the copper accelerator operating at a repetition rate of 120 Hz providing high per-pulse energy as well as the superconducting accelerator operating at a repetition rate of about 1 MHz providing high average intensity. Both accelerators power a soft X-ray free-electron laser with the new variable-gap undulator section. With this flexible light source, TMO supports many experimental techniques not previously available at LCLS and will have two X-ray beam focus spots in line. Thereby, TMO supports atomic, molecular and optical, strong-field and nonlinear science and will also host a designated new dynamic reaction microscope with a sub-micrometer X-ray focus spot. The flexible instrument design is optimized for studying ultrafast electronic and molecular phenomena and can take full advantage of the sub-femtosecond soft X-ray pulse generation program.

Electronic Population Transfer via Impulsive Stimulated X-Ray Raman Scattering with Attosecond Soft-X-Ray Pulses.

Free-electron lasers provide a source of x-ray pulses short enough and intense enough to drive nonlinearities in molecular systems. Impulsive interactions driven by these x-ray pulses provide a way to create and probe valence electron motions with high temporal and spatial resolution. Observing these electronic motions is crucial to understand the role of electronic coherence in chemical processes. A simple nonlinear technique for probing electronic motion, impulsive stimulated x-ray Raman scattering (ISXRS), involves a single impulsive interaction to produce a coherent superposition of electronic states. We demonstrate electronic population transfer via ISXRS using broad bandwidth (5.5 eV full width at half maximum) attosecond x-ray pulses produced by the Linac Coherent Light Source. The impulsive excitation is resonantly enhanced by the oxygen 1s→2π^{*} resonance of nitric oxide (NO), and excited state neutral molecules are probed with a time-delayed UV laser pulse.

Attosecond transient absorption spooktroscopy: a ghost imaging approach to ultrafast absorption spectroscopy.

The recent demonstration of isolated attosecond pulses from an X-ray free-electron laser (XFEL) opens the possibility for probing ultrafast electron dynamics at X-ray wavelengths. An established experimental method for probing ultrafast dynamics is X-ray transient absorption spectroscopy, where the X-ray absorption spectrum is measured by scanning the central photon energy and recording the resultant photoproducts. The spectral bandwidth inherent to attosecond pulses is wide compared to the resonant features typically probed, which generally precludes the application of this technique in the attosecond regime. In this paper we propose and demonstrate a new technique to conduct transient absorption spectroscopy with broad bandwidth attosecond pulses with the aid of ghost imaging, recovering sub-bandwidth resolution in photoproduct-based absorption measurements.

Attosecond coherent electron motion in Auger-Meitner decay.

In quantum systems, coherent superpositions of electronic states evolve on ultrafast time scales (few femtoseconds to attoseconds; 1 attosecond = 0.001 femtoseconds = 10-18 seconds), leading to a time-dependent charge density. Here we performed time-resolved measurements using attosecond soft x-ray pulses produced by a free-electron laser, to track the evolution of a coherent core-hole excitation in nitric oxide. Using an additional circularly polarized infrared laser pulse, we created a clock to time-resolve the electron dynamics and demonstrated control of the coherent electron motion by tuning the photon energy of the x-ray pulse. Core-excited states offer a fundamental test bed for studying coherent electron dynamics in highly excited and strongly correlated matter.