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In molecular systems, the ultrafast motion of electrons initiates the process of chemical change. Tracking this electronic motion across molecules requires coupling attosecond time resolution to atomic-scale spatial sensitivity. In this work, we employ a pair of attosecond x-ray pulses from an x-ray free-electron laser to follow electron motion resulting from the sudden removal of an electron from a prototypical aromatic system, para-aminophenol. X-ray absorption enables tracking this motion with atomic-site specificity. Our measurements are compared with state-of-the-art computational modeling, reproducing the observed response across multiple timescales. Sub-femtosecond dynamics are assigned to states undergoing non-radiative decay, while few-femtosecond oscillatory motion is associated with electronic wavepacket motion in stable cation states, that will eventually couple to nuclear motion. Our work provides insight on the ultrafast charge motion preceding and initiating chemical transformations in moderately complex systems, and provides a powerful benchmark for computational models of ultrafast charge motion in matter.

The photoelectric effect is not truly instantaneous, but exhibits attosecond delays that can reveal complex molecular dynamics. Sub-femtosecond duration light pulses provide the requisite tools to resolve the dynamics of photoionization. Accordingly, the past decade has produced a large volume of work on photoionization delays following single photon absorption of an extreme ultraviolet (XUV) 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. We have now measured the x-ray photoemission delay of core-level electrons, and here report unexpectedly large delays, ranging up to 700 attoseconds in NO near the oxygen K-shell threshold. These measurements exploit attosecond soft x-ray pulses from a free-electron laser (XFEL) to scan across the entire region near the K-shell threshold. Furthermore, we find the delay spectrum is richly modulated, suggesting several contributions including transient trapping of the photoelectron due 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.

Charge migration (CM) is a coherent attosecond process that involves the movement of localized holes across a molecule. To determine the relationship between a molecule's structure and the CM dynamics it exhibits, we perform systematic studies of para-functionalized bromobenzene molecules (X-C$_6$H$_4$-R) using real-time time-dependent density functional theory. We initiate valence-electron dynamics by emulating rapid strong-field ionization leading to a localized hole on the bromine atom. The resulting CM, which takes on the order of 1 fs, occurs via an X localized to C$_6$H$_4$ delocalized to R localized mechanism. Interestingly, the hole contrast on the acceptor functional group increases with increasing electron donating strength. This trend is well-described by the Hammett sigma value of the group, which is a commonly used metric for quantifying the effect of functionalization on the chemical reactivity of benzene derivatives. These results suggest that simple attochemistry principles and a density-based picture can be used to predict and understand CM., Comment: 5 pages, 3 figures

We introduce high-harmonic sideband spectroscopy (HHSS) and show that it can be a robust probe of attosecond charge migration (CM) in a halogenated carbon-chain molecule. We simulate both the CM and harmonic-generation (HHG) dynamics using ab initio time-dependent density-functional theory. We find that CM dynamics initiated along the molecular backbone induces sidebands in the HHG spectrum driven by a delayed laser pulse that is polarized perpendicular to the molecular axis. Monitoring the spectrum as either the HHG laser frequency or the relative delay is scanned allows for the extraction of detailed information about the time-domain characteristics of the CM process., Comment: 8 pages, 7 figures

In quantum systems, coherent superpositions of electronic states evolve on ultrafast timescales (few femtosecond to attosecond, 1 as = 0.001 fs = 10^{-18} s), leading to a time dependent charge density. Here we exploit the first attosecond soft x-ray pulses produced by an x-ray free-electron laser to induce a coherent core-hole excitation in nitric oxide. Using an additional circularly polarized infrared laser pulse we create a clock to time-resolve the electron dynamics, and demonstrate 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.

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., Comment: 13 pages, 3 figures

High-energy, carrier-envelope phase (CEP)-stable, sub-cycle, mid-infrared (mid-IR) pulses can provide unique opportunities of exploring phase-sensitive strong-field light-matter interactions in atoms, molecules, and solids. In the mid-IR wavelength, the ponderomotive energy of laser pulses is dramatically increased (versus the visible/near-infrared) and, therefore, the Keldysh parameter is much smaller than unity even at relatively modest laser intensities. This enables to study the sub-cycle electron dynamics in solids via high-harmonic generation (HHG) without damage. One can also control the electron emissions from nano-devices in the sub-cycle time scale. These efforts are opening a great opportunity towards petahertz electronics. Here, we present a high-energy, sub-cycle pulse synthesizer based on a mid-IR optical parametric amplifier (OPA), pumped by CEP-stable, 2.1 um femtosecond pulses, and its application to HHG in solids. The signal and idler combined spectrum spans from 2.5 to 9.0 um, which covers the whole midwave-infrared (MWIR) region. We coherently synthesize the passively CEP-stable few-cycle signal and idler pulses to generate 33 uJ, 0.88-cycle (12.4 fs), multi-GW pulses centered at ~4.2 um, which is further energy scalable. The in-line synthesis of the CEP-stable sub-cycle pulse is realized through the type-I collinear OPA with minimal temporal walk-off. The MWIR sub-cycle pulse is used for driving HHG in thin silicon samples, producing harmonics up to ~19th order with a continuous spectral coverage due to the isolated emission by the sub-cycle driver. Our demonstration offers an energy scalable and technically simple platform of laser sources generating CEP-stable sub-cycle pulses in the whole MWIR region for investigating isolated phase-sensitive strong-field interactions in solids and gases., Comment: 19 pages, 6 figures

Formation of high spatial frequency laser induced periodic surface structures (HSFL) in germanium by femtosecond mid-IR pulses with wavelengths between $\lambda=2.0$ and $3.6 \; \mathrm{\mu m}$ was studied with varying angle of incidence and polarization. The period of these structures varied from $\lambda/3$ to $\lambda/8$. A modified surface-scattering model including Drude excitation and the optical Kerr effect explains spatial period scaling of HSFL across the mid-IR wavelengths. Transmission electron microscopy (TEM) shows the presence of a $30 \; \mathrm{n m}$ amorphous layer above the structure of crystalline germanium. Various mechanisms including two photon absorption and defect-induced amorphization are discussed as probable causes for the formation of this layer., Comment: 7 pages total (1 page of supplementary material)

We study photoionization of various noble gas atoms by attosecond pulses produced in High Harmonic Generation (HHG). We use a pump-probe experiment to measure the time delays of electrons photoionized from Neon, Argon, and Krypton relative to those photoionized from Helium atoms. The Attosecond Pulse Train (APT) is characterized and the relative delay in photoionization of various noble gases is measured. The photoionization delay of Ne, Ar, and Kr is determined using previously calculated values for the He atomic delay and the delay associated with the probe process., Comment: This paper has been withdrawn by the author because not all of the authors agree/consent to the paper being located on the arxiv