Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrum at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. High-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations.

The quantum mechanical motion of electrons in molecules and solids occurs on the sub-femtosecond timescale. Consequently, the study of ultrafast electronic phenomena requires the generation of laser pulses shorter than 1 fs and of sufficient intensity to interact with their target with high probability.Probing these dynamics with atomic-site specificity requires the extension of sub-femtosecond pulses to the soft X-ray spectral region. Here we report the generation of isolated GW-scale soft X-ray attosecond pulses with an X-ray free-electron laser. Our source has a pulse energy that is six orders of magnitude larger than any other source of isolated attosecond pulses in the soft X-ray spectral region, with a peak power in the tens of gigawatts. This unique combination of high intensity, high photon energy and short pulse duration enables the investigation of electron dynamics with X-ray non-linear spectroscopy and single-particle imaging.their assistance in designing, constructing and installing the XLEAP wiggler. We also acknowledge the SLAC Accelerator Operations group, and the Mechanical and Electrical engineering divisions of the SLAC Accelerator Directorate, especially

Molecules can efficiently and selectively convert light energy into other degrees of freedom. Disentangling the underlying ultrafast motion of electrons and nuclei of the photoexcited molecule presents a challenge to current spectroscopic approaches. Here we explore the photoexcited dynamics of molecules by an interaction with an ultrafast X-ray pulse creating a highly localized core hole that decays via Auger emission. We discover that the Auger spectrum as a function of photoexcitation-X-ray-probe delay contains valuable information about the nuclear and electronic degrees of freedom from an element-specific point of view. For the nucleobase thymine, the oxygen Auger spectrum shifts towards high kinetic energies, resulting from a particular C-O bond stretch in the pp* photoexcited state. A subsequent shift of the Auger spectrum towards lower kinetic energies displays the electronic relaxation of the initial photoexcited state within 200 fs. Ab-initio simulations reinforce our interpretation and indicate an electronic decay to the np* state.

Rapid proton migration is a key process in hydrocarbon photochemistry. Charge migration and subsequent proton motion can mitigate radiation damage when heavier atoms absorb X-rays. If rapid enough, this can improve the fidelity of diffract-before-destroy measurements of biomolecular structure at X-ray-free electron lasers. Here we study X-ray-initiated isomerization of acetylene, a model for proton dynamics in hydrocarbons. Our time-resolved measurements capture the transient motion of protons following X-ray ionization of carbon K-shell electrons. We Coulomb-explode the molecule with a second precisely delayed X-ray pulse and then record all the fragment momenta. These snapshots at different delays are combined into a 'molecular movie' of the evolving molecule, which shows substantial proton redistribution within the first 12 fs. We conclude that significant proton motion occurs on a timescale comparable to the Auger relaxation that refills the K-shell vacancy.

The characterization and conditional preparation of multiphoton quantum states require the use of photonnumber resolving detectors. We study the use of detectors based on multiple avalanche photodiode pixels in this context. We develop a general model that provides the positive operator value measures for these detectors. The model incorporates the effect of cross talk between pixels which is unique to these devices. We validate the model by measuring coherent-state photon-number distributions and reconstructing them with high precision. Finally, we evaluate the suitability of such detectors for quantum state tomography and entanglement-based quantum state preparation, highlighting the effects of dark counts and cross talk between pixels.

Time-resolved femtosecond x-ray diffraction patterns from laser-excited molecular iodine are used to create a movie of intramolecular motion with a temporal and spatial resolution of 30 fs and 0.3 A. This high fidelity is due to interference between the non-stationary excitation and the stationary initial charge distribution. The initial state is used as the local oscillator for heterodyne amplification of the excited charge distribution to retrieve real-space movies of atomic motion onÅngstrom and femtosecond scales. This x-ray interference has not been employed to image internal motion in molecules before. Coherent vibrational motion and dispersion, dissociation, and rotational dephasing are all clearly visible in the data, thereby demonstrating the stunning sensitivity of heterodyne methods.High brightness ultrafast hard x-ray free electron lasers (FELs) can perform time-resolved x-ray diffractive imaging. Recent demonstrations of time-resolved crystal diffraction or time-resolved non-periodic imaging illustrate the power of these sources to trackÅngstrom-scale motion [1,2]. These have spurred new insights in broad areas of science, but have not fully realized the potential of x-ray FELs to image molecules with simultaneous sub-Ångstrom and few-femtosecond resolution. Previous x-ray or electron scattering experiments have used correlations between simulations and data to extract femtosecond molecular dynamics information [3][4][5][6][7].Here we propose and demonstrate an imaging method that employs a universal but unappreciated feature of time-resolved hard x-ray scattering that dramatically improves reconstructed images of charge motion, and enables femtosecond and sub-Ångstrom x-ray movies. The method relies on the "pump-probe" protocol, where motion is initiated by a short "start" pulse, and then interrogated at a later time by a "probe" pulse. The pumped fraction is small, and the unexcited fraction is our heterodyne reference [8].

We demonstrate a single-beam, standoff (>10m) detection and identification of various materials including minute amounts of explosives under ambient light conditions. This is obtained by multiplex coherent anti-Stokes Raman scattering spectroscopy (CARS) using a single femtosecond phase-shaped laser pulse. We exploit the strong nonresonant background for amplification of the backscattered resonant CARS signals by employing a homodyne detection scheme. The simple and highly sensitive spectroscopic technique has a potential for hazardous materials standoff detection applications.

Ultrafast strong-field physics provides insight into quantum phenomena that evolve on an attosecond time scale, the most fundamental of which is quantum tunneling. The tunneling process initiates a range of strong field phenomena such as high harmonic generation (HHG), laser-induced electron diffraction, double ionization and photoelectron holography—all evolving during a fraction of the optical cycle. Here we apply attosecond photoelectron holography as a method to resolve the temporal properties of the tunneling process. Adding a weak second harmonic (SH) field to a strong fundamental laser field enables us to reconstruct the ionization times of photoelectrons that play a role in the formation of a photoelectron hologram with attosecond precision. We decouple the contributions of the two arms of the hologram and resolve the subtle differences in their ionization times, separated by only a few tens of attoseconds.