Characterizing the multi-dimensional reaction dynamics of dihalomethanes using XUV-induced Coulomb explosion imaging.

Site-selective probing of iodine 4d orbitals at 13.1 nm was used to characterize the photolysis of CH2I2 and CH2BrI initiated at 202.5 nm. Time-dependent fragment ion momenta were recorded using Coulomb explosion imaging mass spectrometry and used to determine the structural dynamics of the dissociating molecules. Correlations between these fragment momenta, as well as the onset times of electron transfer reactions between them, indicate that each molecule can undergo neutral three-body photolysis. For CH2I2, the structural evolution of the neutral molecule was simultaneously characterized along the C-I and I-C-I coordinates, demonstrating the sensitivity of these measurements to nuclear motion along multiple degrees of freedom.

Accurate prediction of X-ray pulse properties from a free-electron laser using machine learning.

Free-electron lasers providing ultra-short high-brightness pulses of X-ray radiation have great potential for a wide impact on science, and are a critical element for unravelling the structural dynamics of matter. To fully harness this potential, we must accurately know the X-ray properties: intensity, spectrum and temporal profile. Owing to the inherent fluctuations in free-electron lasers, this mandates a full characterization of the properties for each and every pulse. While diagnostics of these properties exist, they are often invasive and many cannot operate at a high-repetition rate. Here, we present a technique for circumventing this limitation. Employing a machine learning strategy, we can accurately predict X-ray properties for every shot using only parameters that are easily recorded at high-repetition rate, by training a model on a small set of fully diagnosed pulses. This opens the door to fully realizing the promise of next-generation high-repetition rate X-ray lasers.

Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption.

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.Many photo-induced processes such as photosynthesis occur in organic molecules, but their femtosecond excited-state dynamics are difficult to track. Here, the authors exploit the element and site selectivity of soft X-ray absorption to sensitively follow the ultrafast ππ*/nπ* electronic relaxation of hetero-organic molecules.

Self-Referenced Coherent Diffraction X-Ray Movie of Ångstrom- and Femtosecond-Scale Atomic Motion.

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 Å. This high fidelity is due to interference between the nonstationary 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 on ångstrom 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.

Transient impulsive electronic Raman redistribution.

Resonant Raman excitation by ultrafast vacuum ultraviolet laser pulses is a powerful means to study electron dynamics in molecules, but experiments must contend with linear background ionization: frequencies high enough to reach resonant core-valence transitions will usually ionize all occupied orbitals as well, and the ionization cross sections are usually dominant. Here we show that attosecond pulses can induce a process, transient impulsive stimulated Raman scattering, which can overwhelm valence ionization. Calculations are performed for atomic sodium, but the principal is valid for many molecular systems. This approach opens the path for high-fidelity multidimensional spectroscopy with attosecond pulses.

Ultrafast X-ray Auger probing of photoexcited molecular dynamics.

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 ππ* 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 nπ* state.

Remote two-color optical-to-optical synchronization between two passively mode-locked lasers.

Using balanced detection in both the radio frequency (RF) and the optical domain, we remotely synchronize the repetition rate of a Ti:sapphire oscillator to an Er-doped fiber oscillator through a 360 m length-stabilized dispersion compensated fiber link. The drift between these two optical oscillators is 3.3 fs root mean square (rms) over 24 hours. The 68 MHz Er-doped fiber oscillator is locked to a 476 MHz local RF reference clock, and serves as a master clock to distribute 10 fs-level timing signals through stabilized fiber links. This steady remote two-color optical-to-optical synchronization is an important step toward an integrated femtosecond fiber timing distribution system for free-electron lasers (FELs); it does not require x-ray pulses, and it makes sub-10-fs optical/x-ray pump-probe experiments feasible.

On the possibility of enhanced multiple ionization near conical intersections.

Recent measurements of the transient laser-induced fragmentation of photoexcited 1,3-cyclohexadiene undergoing isomerization have seen that some of the fragments have higher velocity at the pump-probe delay corresponding to the time of passage through a conical intersection (Coln). (http://arxiv.org/abs/1212.3728) Here we explore several possible explanations related to the electronic and ionic structure of molecules in the vicinity of Colns and suggest some experimental tests that could illuminate the mechanism and ultimately control this behaviour.

Ultrafast ring opening in 1,3-cyclohexadiene investigated by simplex-based spectral unmixing.

We use spectral unmixing to determine the number of transient photoproducts and to track their evolution following the photo-excitation of 1,3-cyclohexadiene (CHD) to form 1,3,5-hexatriene (HT) in the gas phase. The ring opening is initiated with a 266 nm ultraviolet laser pulse and probed via fragmentation with a delayed intense infrared 800 nm laser pulse. The ion time-of-flight (TOF) spectra are analyzed with a simplex-based spectral unmixing technique. We find that at least three independent spectra are needed to model the transient TOF spectra. Guided by mathematical and physical constraints, we decompose the transient TOF spectra into three spectra associated with the presence of CHD, CHD(+), and HT, and show how these three species appear at different times during the ring opening.

Multiphoton ionization as a clock to reveal molecular dynamics with intense short x-ray free electron laser pulses.

We investigate molecular dynamics of multiple ionization in N2 through multiple core-level photoabsorption and subsequent Auger decay processes induced by intense, short x-ray free electron laser pulses. The timing dynamics of the photoabsorption and dissociation processes is mapped onto the kinetic energy of the fragments. Measurements of the latter allow us to map out the average internuclear separation for every molecular photoionization sequence step and obtain the average time interval between the photoabsorption events. Using multiphoton ionization as a tool of the multiple-pulse pump-probe scheme, we demonstrate the modification of the ionization dynamics as we vary the x-ray laser pulse duration.

Unveiling and driving hidden resonances with high-fluence, high-intensity x-ray pulses.

We show that high fluence, high-intensity x-ray pulses from the world's first hard x-ray free-electron laser produce nonlinear phenomena that differ dramatically from the linear x-ray-matter interaction processes that are encountered at synchrotron x-ray sources. We use intense x-ray pulses of sub-10-fs duration to first reveal and subsequently drive the 1s↔2p resonance in singly ionized neon. This photon-driven cycling of an inner-shell electron modifies the Auger decay process, as evidenced by line shape modification. Our work demonstrates the propensity of high-fluence, femtosecond x-ray pulses to alter the target within a single pulse, i.e., to unveil hidden resonances, by cracking open inner shells energetically inaccessible via single-photon absorption, and to consequently trigger damaging electron cascades at unexpectedly low photon energies.

Nonlinear atomic response to intense ultrashort x rays.

The nonlinear absorption mechanisms of neon atoms to intense, femtosecond kilovolt x rays are investigated. The production of Ne(9+) is observed at x-ray frequencies below the Ne(8+), 1s(2) absorption edge and demonstrates a clear quadratic dependence on fluence. Theoretical analysis shows that the production is a combination of the two-photon ionization of Ne(8+) ground state and a high-order sequential process involving single-photon production and ionization of transient excited states on a time scale faster than the Auger decay. We find that the nonlinear direct two-photon ionization cross section is orders of magnitude higher than expected from previous calculations.

Ultraintense x-ray induced ionization, dissociation, and frustrated absorption in molecular nitrogen.

Sequential multiple photoionization of the prototypical molecule N2 is studied with femtosecond time resolution using the Linac Coherent Light Source (LCLS). A detailed picture of intense x-ray induced ionization and dissociation dynamics is revealed, including a molecular mechanism of frustrated absorption that suppresses the formation of high charge states at short pulse durations. The inverse scaling of the average target charge state with x-ray peak brightness has possible implications for single-pulse imaging applications.

Auger electron angular distribution of double core-hole states in the molecular reference frame.

The Linac Coherent Light Source free electron laser is a source of high brightness x rays, 2×10(11) photons in a ∼5 fs pulse, that can be focused to produce double core vacancies through rapid sequential ionization. This enables double core vacancy Auger electron spectroscopy, an entirely new way to study femtosecond chemical dynamics with Auger electrons that probe the local valence structure of molecules near a specific atomic core. Using 1.1 keV photons for sequential x-ray ionization of impulsively aligned molecular nitrogen, we observed a rich single-site double core vacancy Auger electron spectrum near 413 eV, in good agreement with ab initio calculations, and we measured the corresponding Auger electron angle dependence in the molecular frame.

Double core-hole production in N2: beating the Auger clock.

We investigate the creation of double K-shell holes in N2 molecules via sequential absorption of two photons on a time scale shorter than the core-hole lifetime by using intense x-ray pulses from the Linac Coherent Light Source free electron laser. The production and decay of these states is characterized by photoelectron spectroscopy and Auger electron spectroscopy. In molecules, two types of double core holes are expected, the first with two core holes on the same N atom, and the second with one core hole on each N atom. We report the first direct observations of the former type of core hole in a molecule, in good agreement with theory, and provide an experimental upper bound for the relative contribution of the latter type.

Time-resolved pump-probe experiments at the LCLS.

The first time-resolved x-ray/optical pump-probe experiments at the SLAC Linac Coherent Light Source (LCLS) used a combination of feedback methods and post-analysis binning techniques to synchronize an ultrafast optical laser to the linac-based x-ray laser. Transient molecular nitrogen alignment revival features were resolved in time-dependent x-ray-induced fragmentation spectra. These alignment features were used to find the temporal overlap of the pump and probe pulses. The strong-field dissociation of x-ray generated quasi-bound molecular dications was used to establish the residual timing jitter. This analysis shows that the relative arrival time of the Ti:Sapphire laser and the x-ray pulses had a distribution with a standard deviation of approximately 120 fs. The largest contribution to the jitter noise spectrum was the locking of the laser oscillator to the reference RF of the accelerator, which suggests that simple technical improvements could reduce the jitter to better than 50 fs.

Femtosecond electronic response of atoms to ultra-intense X-rays.

An era of exploring the interactions of high-intensity, hard X-rays with matter has begun with the start-up of a hard-X-ray free-electron laser, the Linac Coherent Light Source (LCLS). Understanding how electrons in matter respond to ultra-intense X-ray radiation is essential for all applications. Here we reveal the nature of the electronic response in a free atom to unprecedented high-intensity, short-wavelength, high-fluence radiation (respectively 10(18) W cm(-2), 1.5-0.6 nm, approximately 10(5) X-ray photons per A(2)). At this fluence, the neon target inevitably changes during the course of a single femtosecond-duration X-ray pulse-by sequentially ejecting electrons-to produce fully-stripped neon through absorption of six photons. Rapid photoejection of inner-shell electrons produces 'hollow' atoms and an intensity-induced X-ray transparency. Such transparency, due to the presence of inner-shell vacancies, can be induced in all atomic, molecular and condensed matter systems at high intensity. Quantitative comparison with theory allows us to extract LCLS fluence and pulse duration. Our successful modelling of X-ray/atom interactions using a straightforward rate equation approach augurs favourably for extension to complex systems.

Strongly dispersive transient Bragg grating for high harmonics.

We create a transient Bragg grating in a high-harmonic generation medium using two counterpropagating pulses. The Bragg grating disperses the harmonics in angle and can diffract a large bandwidth with temporal resolution limited only by the source size.

Calibration of a high harmonic spectrometer by laser induced plasma emission.

We present a method that allows for a convenient switching between high harmonic generation (HHG) and accurate calibration of the vacuum ultraviolet (VUV) spectrometer used to analyze the harmonic spectrum. The accurate calibration of HHG spectra is becoming increasingly important for the determination of electronic structures. The wavelength of the laser harmonics themselves depend on the details of the harmonic geometry and phase matching, making them unsuitable for calibration purposes. In our calibration mode, the target resides directly at the focus of the laser, thereby enhancing plasma emission and suppressing harmonic generation. In HHG mode, the source medium resides in front or after the focus, showing enhanced HHG and no plasma emission lines. We analyze the plasma emission and use it for a direct calibration of our HHG spectra.