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Philip H. Bucksbaum

Publications and source records attributed to Philip H. Bucksbaum.

At least 19 recordsLinked to original sources

Electron spectra from strong-field enhanced ionization in heavy water

Strong-field enhanced ionization (EI) is a phenomenon in which stretching of interatomic bonds into a distorted molecular geometry leads to an increase in the tunneling ionization rate driven by a strong field. While the nuclear dynamics leading to EI are well established, the electron dynamics of the ionization step remain largely unexplored. Isolating the momentum distribution of the electrons involved in EI is critical to fully characterizing the phenomenon. We have measured the electron momentum distribution associated with EI in triple ionization of D$_2$O using 6-fs pulse pairs together with full fragment momentum imaging and electron-ion correlation methods. We find that the EI electron momentum distribution differs substantially from that of standard strong-field tunneling from molecules, exhibiting an increased yield of electrons with large momentum in the direction of the laser polarization, and a change from the expected Gaussian distribution. These observations indicate that the instantaneous EI tunneling rate is maximized at a critical value of the laser electric field, rather than at the peak of an optical cycle. This finding distinguishes EI from Keldysh tunneling rate predictions, where tunneling rate increases monotonically with field strength. These pronounced differences between EI and non-EI electron spectra are critical tests of models of enhanced ionization and suggest a route towards control of the sub-cycle timing of electron emission.

physics.atom-ph

Tracking molecular hydrogen formation from ionized water in real time

Removing an electron from a water molecule can drive its two hydrogen atoms to pair up and depart as molecular hydrogen. However, even for this elementary reaction, the route from start to finish has remained hidden because measurements have yet to follow the electronic and nuclear motion simultaneously. Combining correlated photoelectron and ion imaging, few-femtosecond pump--probe measurements, and nonadiabatic simulations, we track the complete pathway in isolated heavy water (D$_2$O) molecules. The reaction takes an indirect route and dissociates along three distinct pathways (direct, roaming, and delayed) with formation times of about 34 and 72 femtoseconds for the direct and delayed branches. Yet bond formation requires the molecule to first break its own symmetry. Only random asymmetric motion enables the electronic-state switch at a conical intersection, joining the two hydrogen atoms before the oxygen--hydrogen bond breaks. These results establish a time-resolved picture of molecular hydrogen formation from water and provide a general strategy for linking electronic excitation to chemical outcomes in settings from radiation damage to hydrogen production.

physics.chem-ph

Fast array-based particle coincidence detection in a TimePix3-based velocity map imaging instrument

With the development of high repetition rate laser sources and advanced multi-particle correlation analyses such as covariance mapping, particle detection techniques such as velocity map imaging (VMI) are poised to offer unprecedented views into molecular phenomena. Taking full advantage of the high count rates in these experiments requires the development of detectors with sufficient spatial and temporal resolution that can process data in real time. The TimePix3 camera (TPX3CAM) is an event-based pixel detector capable of spatio-temporally localizing many simultaneous particle hits in an efficient manner. While the sparse nature of the data stream allows for compact representation of particle hits, it also presents algorithmic and computational challenges for clustering individual pixels into hits. Here we present the theory and application of a rapid data processing and centroiding algorithm for ion and electron hits collected in a VMI instrument. The array-based computations that comprise the algorithm take full advantage of the data sparsity of the TimePix3 data stream and localize particle hits on the microchannel plate (MCP) to better than a single pixel on the pixel detector. Centroiding can be parallelized on a commercially available graphics processing unit (GPU) for additional speed. Using these innovations, data processing occurs about 25 times faster than data acquisition, for a 1 kHz repetition rate instrument and tens of particles per shot. In addition to its speed, the TPX3CAM detector outperforms state-of-the-art delay line anode detectors at discriminating multiple simultaneous hits, enabling high-fidelity coincidence and covariance studies in the near future.

physics.ins-det

Optical Interference Effect in Strong-field Electronic Coherence Spectroscopy

We have investigated strong-field-induced electronic coherences in argon and molecular nitrogen ions created by high-intensity, few-cycle infrared laser pulses. This is a step toward the long-sought goal of strong-field coherent control in molecular chemistry. We employed high-intensity, few-cycle infrared laser pulses in a pump-probe setup to investigate a recent prediction that electronic coherences in nitrogen molecules change the ion yields vs. pump-probe delay. [Yuen and Lin, Phys. Rev. A 109, L011101 (2024)]. The predicted coherence signals in molecular nitrogen could not be resolved above the optical interference of the pump and probe pulses; a simultaneous measurement clearly resolved the induced cation fine-structure coherence in strong-field-ionized argon. The results of our comparison with simulations suggest that optical interference effects manifest differently in each ionic species and must be carefully accounted for when interpreting experimental data. We found that nonsequential double ionization in the low-intensity region of the focal volume can reduce the visibility of coherence generated by two-pulse sequential ionization, and we quantify the importance of pulse shape and spectral characteristics for isolating the desired coherence signals.

physics.atom-ph

Imaging valence electron rearrangement in a chemical reaction using hard X-ray scattering

We have observed the signatures of valence electron rearrangement in photoexcited ammonia using ultrafast hard X-ray scattering. Time-resolved X-ray scattering is a powerful tool for imaging structural dynamics in molecules because of the strong scattering from the core electrons localized near each nucleus. Such core-electron contributions generally dominate the differential scattering signal, masking any signatures of rearrangement in the chemically important valence electrons. Ammonia represents an exception to the typically high core-to-valence electron ratio. We measured 9.8 keV X-ray scattering from gas-phase deuterated ammonia following photoexcitation via a 200 nm pump pulse to the 3s Rydberg state. We observed changes in the recorded scattering patterns due to the initial photoexcitation and subsequent deuterium dissociation. Ab initio calculations confirm that the observed signal is sensitive to the rearrangement of the single photoexcited valence electron as well as the interplay between adiabatic and nonadiabatic dissociation channels. The use of ultrafast hard X-ray scattering to image the structural rearrangement of single valence electrons constitutes an important advance in tracking valence electronic structure in photoexcited atoms and molecules.

physics.chem-ph

Covariance Analysis of Impulsive Streaking

We present a comprehensive framework of modeling covariance in angular streaking experiments. Within the impulsive streaking regime, the displacement of electron momentum distribution (MD) provides a tight connection between the dressing-free MD and the dressed MD. Such connection establishes universal structures in the composition of streaking covariance that are common across different MDs, regardless of their exact shape. Building on this robust framework, we have developed methods for retrieving temporal information from angular streaking measurements. By providing a detailed understanding of the covariance structure in angular streaking experiments, our work enables more accurate and robust temporal measurements in a wide range of experimental scenarios.

physics.data-an

Attosecond Coherent Electron Motion in a Photoionized Aromatic Molecule

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.

physics.chem-ph

Isotope-Selective Strong Field Ionization of Semi-Heavy Water

Semi-heavy water (HOD) is one of the simplest molecules in which the bonds are labelled by isotope. We demonstrate that a pair of intense few-femtosecond infrared laser pulses can be used to selectively tunnel ionize along one of the two bonds. The first pulse doubly ionizes HOD, inducing rapid bond stretching and unbending. Femtoseconds later, the second pulse arrives and further ionization is selectively enhanced along the OH bond. These conclusions arise from 3D time-resolved measurements of H$^+$, D$^+$, and O$^+$ momenta following triple ionization.

physics.chem-ph

Attosecond Delays in X-ray Molecular Ionization

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.

physics.atom-ph

Experimental Demonstration of Attosecond Pump-Probe Spectroscopy with an X-ray Free-Electron Laser

Pump-probe experiments with sub-femtosecond resolution are the key to understanding electronic dynamics in quantum systems. Here we demonstrate the generation and control of sub-femtosecond pulse pairs from a two-colour X-ray free-electron laser (XFEL). By measuring the delay between the two pulses with an angular streaking diagnostic, we characterise the group velocity of the XFEL and demonstrate control of the pulse delay down to 270 as. We demonstrate the application of this technique to a pump-probe measurement in core-excited para-aminophenol. These results demonstrate the ability to perform pump-probe experiments with sub-femtosecond resolution and atomic site specificity.

physics.acc-ph

Femtosecond pulse parameter estimation from photoelectron momenta using machine learning

Deep learning models have provided huge interpretation power for image-like data. Specifically, convolutional neural networks (CNNs) have demonstrated incredible acuity for tasks such as feature extraction or parameter estimation. Here we test CNNs on strong-field ionization photoelectron spectra, training on theoretical data sets to `invert' experimental data. Pulse characterization is used as a `testing ground', specifically we retrieve the laser intensity, where `traditional' measurements typically lead to 20% uncertainty. We report on crucial data augmentation techniques required to successfully train on theoretical data and return consistent results from experiments, including accounting for detector saturation. The same procedure can be repeated to apply CNNs in a range of scenarios for strong-field ionization. Using a predictive uncertainty estimation, reliable laser intensity uncertainties of a few percent can be extracted, which are consistently lower than those given by traditional techniques. Using interpretability methods can reveal parts of the distribution that are most sensitive to laser intensity, which can be directly associated with holographic interferences. The CNNs employed provide an accurate and convenient ways to extract parameters, and represent a novel interpretational tool for strong-field ionization spectra.

physics.atom-ph

Photon Energy-Resolved Velocity Map Imaging from Spectral Domain Ghost Imaging

We present an approach that combines photon spectrum correlation analysis with the reconstruction of three-dimensional momentum distribution from velocity map images in an efficient, single-step procedure. We demonstrate its efficacy with the results from the photoionization of the $2p$-shell of argon using the FLASH free-electron laser~(FEL). Distinct spectral features due to the spin-orbit splitting of Ar$^+(2p^{-1})$ are resolved, despite the large average bandwidth of the ionizing pulses from the FEL. This demonstrates a clear advantage over the conventional analysis method, and it will be broadly beneficial for velocity map imaging experiments with FEL sources. The retrieved linewidth of the binding energy spectrum approaches the resolution limitation prescribed by the spectrometers used to collect the data. Our approach presents a path to extend spectral-domain ghost imaging to the case where the photoproduct observable is high-dimensional.

physics.atom-ph

Femtosecond electronic and hydrogen structural dynamics in ammonia imaged with ultrafast electron diffraction

Directly imaging structural dynamics involving hydrogen atoms by ultrafast diffraction methods is complicated by their low scattering cross-sections. Here we demonstrate that megaelectronvolt ultrafast electron diffraction is sufficiently sensitive to follow hydrogen dynamics in isolated molecules. In a study of the photodissociation of gas phase ammonia, we simultaneously observe signatures of the nuclear and corresponding electronic structure changes resulting from the dissociation dynamics in the time-dependent diffraction. Both assignments are confirmed by ab initio simulations of the photochemical dynamics and the resulting diffraction observable. While the temporal resolution of the experiment is insufficient to resolve the dissociation in time, our results represent an important step towards the observation of proton dynamics in real space and time.

physics.chem-ph

Time Correlation Filtering Reveals Two-Path Electron Quantum Interference in Strong-Field Ionization

Attosecond dynamics in strong-field tunnel ionization are encoded in intricate holographic patterns in the photoelectron momentum distributions (PMDs). These patterns show the interference between two or more superposed quantum electron trajectories, which are defined by their ionization times and subsequent evolution in the laser field. We determine the ionization time separation between interfering pairs of electron orbits by performing a differential Fourier analysis on the measured momentum spectrum. We identify electron holograms formed by trajectory pairs whose ionization times are separated by less than a single quarter cycle, between a quarter cycle and half cycle, between a half cycle and three fourths of a cycle, and a full cycle apart. We compare our experimental results to the predictions of the Coulomb quantum orbit strong-field approximation (CQSFA), with significant success. We also time-filter the CQSFA trajectory calculations to demonstrate the validity of the technique on spectra with known time correlations. As a general analysis technique, the filter can be applied to all energy- and angularly-resolved datasets to recover time correlations between interfering electron pathways, providing an important tool to analyze any strong-field ionization spectra.

physics.atom-ph

Attosecond Coherent Electron Motion in Auger-Meitner Decay

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.

physics.chem-ph

Strong Field Ionization of Water II: Electronic and Nuclear Dynamics En Route to Double Ionization

We investigate the role of nuclear motion and strong-field-induced electronic couplings during the double ionization of deuterated water using momentum-resolved coincidence spectroscopy. By examining the three-body dicationic dissociation channel, D$^{+}$/D$^{+}$/O, for both few- and multi-cycle laser pulses, strong evidence for intra-pulse dynamics is observed. The extracted angle- and energy-resolved double ionization yields are compared to classical trajectory simulations of the dissociation dynamics occurring from different electronic states of the dication. In contrast with measurements of single photon double ionization, pronounced departure from the expectations for vertical ionization is observed, even for pulses as short as 10~fs in duration. We outline numerous mechanisms by which the strong laser field can modify the nuclear wavefunction en-route to final states of the dication where molecular fragmentation occurs. Specifically, we consider the possibility of a coordinate-dependence to the strong-field ionization rate, intermediate nuclear motion in monocation states prior to double ionization, and near-resonant laser-induced dipole couplings in the ion. These results highlight the fact that, for small and light molecules such as D$_2$O, a vertical-transition treatment of the ionization dynamics is not sufficient to reproduce the features seen experimentally in the strong field coincidence double-ionization data.

physics.atom-ph

Dissecting Sub-Cycle Interference in Photoelectron Holography

Multipath holographic interference in strong-field quantum tunnel ionization is key to revealing sub-Angstrom attosecond dynamics for molecular movies. This critical sub-cycle motion is often obscured by longer time-scale effects such as ring-shaped patterns that appear in above-threshold ionization (ATI). In the present work, we overcome this problem by combining two novel techniques in theory and experimental analysis: unit-cell averaging and time-filtering data and simulations. Together these suppress ATI rings and enable an unprecedented highly-detailed quantitative match between strong-field ionization experiments in argon and the Coulomb-quantum orbit strong-field approximation (CQSFA) theory. Velocity map images reveal fine modulations on the holographic spider-like interference fringes that form near the polarization axis. CQSFA theory traces this to the interference of three types of electron pathways. The level of agreement between experiment and theory allows sensitive determination of quantum phase differences and symmetries, providing an important tool for quantitative dynamical imaging in quantum systems.

physics.atom-ph

Resolving Multiphoton Processes with High-Order Anisotropy Ultrafast X-ray Scattering

We present first results on ultrafast X-ray scattering of strongly driven molecular Iodine and analysis of high-order anisotropic components of the scattering signal, up to four-photon absorption. We discuss the technical details of retrieving high fidelity high-order anisotropy components, and outline a method to analyze the scattering signal using Legendre decomposition. We use simulated anisotropic scattering signals and Fourier analysis to map how anisotropic dissociation motions can be extracted from the various Legendre orders. We observe multitude dissociation and vibration motions simultaneously arising from various multiphoton transitions. We use the anisotropy information of the scattering signal to disentangle the different processes and assign their dissociation velocities on the Angstrom and femtosecond scales de-novo.

physics.atom-ph