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We propose a quantum tomography (QT) approach to retrieve the temporally evolving reduced density matrix in electronic state basis, where the populations and coherence between the ground state and excited state are reconstructed from the ultrafast electron diffraction signal. In order to showcase the capability of the proposed QT approach, we simulate the nuclear wavepacket dynamics and ultrafast electron diffraction of photoexcited pyrrole molecules using the ab initio quantum chemical CASSCF method. From the simulated time-resolved diffraction data, we retrieve the evolving density matrix in a crude diabatic representation basis and reveal the symmetry of the excited pyrrole wavepacket. Our QT approach opens the route to make a quantum version of "molecular movie" that covers the electronic degree of freedom and equips ultrafast electron diffraction with the power to reveal the coherence between electronic states, relaxation, and dynamics of population transfer. [ABSTRACT FROM AUTHOR]

Inferring transient molecular structural dynamics from diffraction data is an ambiguous task that often requires different approximation methods. In this paper, we present an attempt to tackle this problem using machine learning. Although most recent applications of machine learning for the analysis of diffraction images apply only a single neural network to an experimental dataset and train it on the task of prediction, our approach utilizes an additional generator network trained on both synthetic and experimental data. Our network converts experimental data into idealized diffraction patterns from which information is extracted via a convolutional neural network trained on synthetic data only. We validate this approach on ultrafast electron diffraction data of bismuth samples undergoing thermalization upon excitation via 800 nm laser pulses. The network was able to predict transient temperatures with a deviation of less than 6% from analytically estimated values. Notably, this performance was achieved on a dataset of 408 images only. We believe that employing this network in experimental settings where high volumes of visual data are collected, such as beam lines, could provide insights into the structural dynamics of different samples. [ABSTRACT FROM AUTHOR]

For time-resolved diffraction studies of irreversible structural dynamics upon photoexcitation, there are constraints on the number of perturbation cycles due to thermal effects and accumulated strain, which impact the degree of crystal order and spatial resolution. This problem is exasperated for surface studies that are more prone to disordering and defect formation. Ultrafast electron diffraction studies of these systems, with the conventional stroboscopic pump–probe protocol, require repetitive measurements on well-prepared diffraction samples to acquire and average signals above background in the dynamic range of interest from few tens to hundreds of picoseconds. Here, we present ultrafast streaked low-energy electron diffraction (LEED) that demands, in principle, only a single excitation per nominal data acquisition timeframe. By exploiting the space–time correlation characteristics of the streaking method and high-charge 2 keV electron bunches in the transmission geometry, we demonstrate about one order of magnitude reduction in the accumulated number of the excitation cycles and total electron dose, and 48% decrease in the root mean square error of the model fit residual compared to the conventional time-scanning measurement. We believe that our results demonstrate a viable alternative method with higher sensitivity to that of nanotip-based ultrafast LEED studies relying on a few electrons per a single excitation, to access to all classes of structural dynamics to provide an atomic level view of surface processes. [ABSTRACT FROM AUTHOR]

Samples suitable for electron diffraction studies must satisfy certain characteristics such as having a thickness in the range of 10–100 nm. We report, to our knowledge, the first successful synthesis technique of nanometer-thin sheets of single-crystalline thymine suitable for electron diffraction and spectroscopy studies. This development provides a well-defined system to explore issues related to UV photochemistry of DNA and high intrinsic stability essential to maintaining integrity of genetic information. The crystals are grown using the evaporation technique, and the nanometer-thin sheets are obtained via microtoming. The sample is characterized via x-ray diffraction and is subsequently studied using electron diffraction via a transmission electron microscope. Thymine is found to be more radiation resistant than similar molecular moieties (e.g., carbamazepine) by a factor of 5. This raises interesting questions about the role of the fast relaxation processes of electron scattering-induced excited states, extending the concept of radiation hardening beyond photoexcited states. The high stability of thymine in particular opens the door for further studies of these ultrafast relaxation processes giving rise to the high stability of DNA to UV radiation. [ABSTRACT FROM AUTHOR]

The development of electron sources capable of temporal resolution on the order of 1 ps or less raises a number of questions associated with the estimation of the physical meaning and accuracy of the dynamic parameters based on the analysis of time-dependent scattering intensity. The use of low brightness ultrashort pulses with few electrons leads to the necessity for increasing the total exposure time and lengthening the time of data acquisition, with attendant problems with the limited sample. The sample restrictions can be mitigated by increasing the charge per pulse, i.e., by going to high brightness sources. Increasing in the number of electrons, however, is limited by the Coulomb repulsion between them, which leads on one hand to distortion of the diffraction pattern and on the other hand to an increase in the duration of the pulse. An analytical technique for estimating the deformation of the diffraction pattern caused by the Coulomb repulsion of the electrons in electron bunches with duration of less than 10 ps and the influence of this effect on the accuracy of determination of the interatomic distances is developed for the non-relativistic and relativistic regimes for electron energies. [ABSTRACT FROM AUTHOR]

Thin single organic crystals (≤1 μm) with large area (≥100 × 100 μm2) are desirable to explore photoinduced processes using ultrafast spectroscopy and electron-diffraction. Here, we present a general method based on spatial confinement to grow such crystals using the prototypical proton transfer system, 1,5-dihydroxyanthraquinone, as an example, and provide the protocol for optically characterizing structural dynamics to enable proper assignments using diffraction methods. [ABSTRACT FROM AUTHOR]

Here, we report on a new approach based on laser driven molecular beams that provides simultaneously nanoscale liquid droplets and gas-phase sample delivery for femtosecond electron diffraction studies. The method relies on Picosecond InfraRed Laser (PIRL) excitation of vibrational modes to strongly drive phase transitions under energy confinement by a mechanism referred to as Desorption by Impulsive Vibrational Excitation (DIVE). This approach is demonstrated using glycerol as the medium with selective excitation of the OH stretch region for energy deposition. The resulting plume was imaged with both an ultrafast electron gun and a pulsed bright-field optical microscope to characterize the sample source simultaneously under the same conditions with time synchronization equivalent to sub-micrometer spatial resolution in imaging the plume dynamics. The ablation front gives the expected isolated gas phase, whereas the trailing edge of the plume is found to consist of nanoscale liquid droplets to thin films depending on the excitation conditions. Thus, it is possible by adjusting the timing to go continuously from probing gas phase to solution phase dynamics in a single experiment with 100% hit rates and very low sample consumption (<100 nl per diffraction image). This approach will be particularly interesting for biomolecules that are susceptible to denaturation in turbulent flow, whereas PIRL–DIVE has been shown to inject molecules as large as proteins into the gas phase fully intact. This method opens the door as a general approach to atomically resolving solution phase chemistry as well as conformational dynamics of large molecular systems and allow separation of the solvent coordinate on the dynamics of interest. [ABSTRACT FROM AUTHOR]

Ultrafast electron diffraction and time-resolved serial crystallography are the basis of the ongoing revolution in capturing at the atomic level of detail the structural dynamics of molecules. However, most experiments capture only the probability density of the nuclear wavepackets to determine the time-dependent molecular structures, while the full quantum state has not been accessed. Here, we introduce a framework for the preparation and ultrafast coherent diffraction from rotational wave packets of molecules, and we establish a new variant of quantum state tomography for ultrafast electron diffraction to characterize the molecular quantum states. The ability to reconstruct the density matrix, which encodes the amplitude and phase of the wavepacket, for molecules of arbitrary degrees of freedom, will enable the reconstruction of a quantum molecular movie from experimental x-ray or electron diffraction data. Ultrafast diffraction is fundamental in capturing the structural dynamics of molecules. Here, the authors establish a variant of quantum state tomography for arbitrary degrees of freedom to characterize the molecular quantum states, which will enable the reconstruction of a quantum molecular movie from diffraction data. [ABSTRACT FROM AUTHOR]

One of the most basic molecular photophysical processes is that of spin transitions and intersystem crossing between excited states surfaces. The change in spin states affects the spatial distribution of electron density through the spin orbit coupling interaction. The subsequent nuclear reorganization reports on the full extent of the spin induced change in electron distribution, which can be treated similarly to intramolecular charge transfer with effective reaction coordinates depicting the spin transition. Here, single-crystal [FeII(bpy)3](PF6)2, a prototypical system for spin crossover (SCO) dynamics, is studied using ultrafast electron diffraction in the single-photon excitation regime. The photoinduced SCO dynamics are resolved, revealing two distinct processes with a (450 ± 20)-fs fast component and a (2.4 ± 0.4)-ps slow component. Using principal component analysis, we uncover the key structural modes, ultrafast Fe–N bond elongations coupled with ligand motions, that define the effective reaction coordinate to fully capture the relevant molecular reorganization. Electron spin is a fundamental property of molecules, and changes in spin state affect both molecular structure and dynamics. Here, the authors resolve, by ultrafast electron diffraction, the nuclear reorganization stabilizing spin transitions in a [FeII(bpy)3](PF6)2 crystal. [ABSTRACT FROM AUTHOR]

Here, we present an optical fiber-based electron gun designed for the ultrafast streaking of low-energy electron bunches. The temporal profile of the few tens of the picosecond long electron bunch composed of 200 electrons is well characterized using a customized streak camera. Detailed analysis reveals that the stretched optical trigger pulse owing to the dispersion effects inside the waveguide dominantly determines the temporal length of the low density electron bunch. This result illustrates the capability to control the observable time-window in the streak diffraction experiment by tailoring geometrical parameters of the fiber source and its coupling condition. With the electrostatic Einzel lens system integrated on the fiber-based cathode, we also demonstrate spatial focusing of the electron beam with the RMS spot size of 98 μm and imaging of the static low-energy electron diffraction pattern of monolayer graphene in the electron kinetic energy range of 1.0–2.0 keV. [ABSTRACT FROM AUTHOR]

We explore the spatial coherence of double-gate single nanotip field emitters by low-energy electron diffraction experiments in transmission mode. By producing collimated field emission pulses from the single nanotip cathode and irradiating a suspended monolayer graphene film without additional optics, we observed sharper and higher resolution Bragg diffraction spots than a previous experiment using a nanotip array cathode. In particular, we found complete conservation of the size and the shape of the diffraction spots with those of the incident beam on the sample. The result indicates that the transverse coherence of a nanofabricated double-gate single-tip emitter is much larger than a few nanometers as determined by the apparent diffraction spot size and overall spatial resolution of the observed diffraction pattern. [ABSTRACT FROM AUTHOR]

In conjunction with ultrafast diffraction, streak cameras offer an unprecedented opportunity for recording an entire molecular movie with a single probe pulse. This is an attractive alternative to conventional pump-probe experiments and opens the door to studying irreversible dynamics. However, due to the "smearing" of the diffraction pattern across the detector, the streaking technique has thus far been limited to simple mono-crystalline samples and extreme care has been taken to avoid overlapping diffraction spots. In this article, this limitation is addressed by developing a general theory of streaking of time-dependent diffraction patterns. Understanding the underlying physics of this process leads to the development of an algorithm based on Bayesian analysis to reconstruct the time evolution of the two-dimensional diffraction pattern from a single streaked image. It is demonstrated that this approach works on diffraction peaks that overlap when streaked, which not only removes the necessity of carefully choosing the streaking direction but also extends the streaking technique to be able to study polycrystalline samples and materials with complex crystalline structures. Furthermore, it is shown that the conventional analysis of streaked diffraction can lead to erroneous interpretations of the data. [ABSTRACT FROM AUTHOR]

We present an RF gun design for single shot ultrafast electron diffraction experiments that can produce sub-100 fs high-charge electron bunches in the 130 keV energy range. Our simulations show that our proposed half-cell RF cavity is capable of producing 137 keV, 27 fs rms (60 fs FWHM), 106 electron bunches with an rms spot size of 276 lm and a transverse coherence length of 2.0 nm. The required operation power is 9.2 kW, significantly lower than conventional rf cavity designs and a key design feature. This electron source further relies on high electric field gradients at the cathode to simultaneously accelerate and compress the electron bunch to open up new space-time resolution domains for atomically resolved dynamics. [ABSTRACT FROM AUTHOR]

Photoexcitation of spin crossover (SCO) complexes can trigger extensive electronic spin transitions and transformation of molecular structure. However, the precise nature of the associated ultrafast structural dynamics remains elusive, especially in the solid state. Here, we studied a single-crystal SCO material with femtosecond electron diffraction (FED). The unique capability of FED allows us to directly probe atomic motions and to track ultrafast structural changes within a crystal lattice. By monitoring the time-dependent changes of the Bragg reflections, we observed the formation of a photoinduced structure similar to the thermally induced high-spin state. The data and refinement calculations indicate the global structural reorganization within 2.3 ps, as the metal-ligand bond distribution narrows during intramolecular vibrational energy redistribution (IVR) driving the intermolecular rearrangement. Three independent dynamical group are identified to model the structural dynamics upon photoinduced SCO. [ABSTRACT FROM AUTHOR]

Solvated iron(II)-tris(bipyridine) ([FeII(bpy)3]2+) has been extensively studied with regard to the spin crossover (SCO) phenomenon. Herein, the ultrafast spin transition dynamics of single crystal [FeII(bpy)3](PF6)2 was characterized for the first time using femtosecond transient absorption (TA) spectroscopy. The single crystal environment is of interest for experiments that probe the nuclear motions involved in the SCO transition, such as femtosecond X-ray and electron diffraction. We found that the TA at early times is very similar to what has been reported in solvated [FeII(bpy)3]2+, whereas the later dynamics are perturbed in the crystal environment. The lifetime of the high-spin state is found to be much shorter (100 ps) than in solution due to chemical pressure exerted by the lattice. Oscillatory behavior was observed on both time scales. Our results show that single crystal [FeII(bpy)3](PF6)2 serves as an excellent model system for localized molecular spin transitions. [ABSTRACT FROM AUTHOR]

Ultrafast processes can now be studied with the combined atomic spatial resolution of diffraction methods and the temporal resolution of femtosecond optical spectroscopy by using femtosecond pulses of electrons or hard X-rays as structural probes. However, it is challenging to apply these methods to organic materials, which have weak scattering centres, thermal lability, and poor heat conduction. These characteristics mean that the source needs to be extremely bright to enable us to obtain high-quality diffraction data before cumulative heating effects from the laser excitation either degrade the sample or mask the structural dynamics. Here we show that a recently developed, ultrabright femtosecond electron source makes it possible to monitor the molecular motions in the organic salt (EDO-TTF)2PF6 as it undergoes its photo-induced insulator-to-metal phase transition. After the ultrafast laser excitation, we record time-delayed diffraction patterns that allow us to identify hundreds of Bragg reflections with which to map the structural evolution of the system. The data and supporting model calculations indicate the formation of a transient intermediate structure in the early stage of charge delocalization (less than five picoseconds), and reveal that the molecular motions driving its formation are distinct from those that, assisted by thermal relaxation, convert the system into a metallic state on the hundred-picosecond timescale. These findings establish the potential of ultrabright femtosecond electron sources for probing the primary processes governing structural dynamics with atomic resolution in labile systems relevant to chemistry and biology. [ABSTRACT FROM AUTHOR]

We present the design of a back-illuminated photocathode for electron diffraction experiments based on an optical fiber, and experimental characterization of emitted electron bunches. Excitation light is guided through the fiber into the experimental vacuum chamber, eliminating typical alignment difficulties between the emitter metal and the optical trigger and position instabilities, as well as providing reliable control of the laser spot size and profile. The in-vacuum fiber end is polished and coated with a 30 nm gold (Au) layer on top of 3 nm of chromium (Cr), which emits electrons by means of single-photon photoemission when femtosecond pulses in the near ultraviolet (257 nm) are fed into the fiber on the air side. The emission area can be adjusted to any value between a few nanometers (using tapered fibers) and the size of a multi-mode fiber core (100 lm or larger). In this proof-of-principle experiment, two different types of fibers were tested, with emission spot diameters of 50 lm and 100 lm, respectively. The normalized thermal electron beam emittance (TE) was measured by means of the aperture scan technique, and a TE of 4.0 p nm was measured for the smaller spot diameter. Straightforward enhancements to the concept allowed to demonstrate operation in an electric field environment of up to 7 MV/m. [ABSTRACT FROM AUTHOR]

This paper provides a practical introduction to the current practice of femtosecond electron diffraction. We emphasize a general implementation suitable for a wide class of photoactive samples, including nonreversible samples. High density femtosecond electron pulses are required and the consequences for diffractometer design and sample preparation and handling are discussed. Finally, the real space structural analysis of strongly-driven melting in metals possible with our implementation is outlined. [ABSTRACT FROM AUTHOR]

Femtosecond electron diffraction (FED) is a new technique within the still-developing field of ultrafast diffraction. This paper presents an outline of the basic features of FED, including a brief history of its development in terms of the technical challenges of working with femtosecond electron pulses and the ultrathin samples required. Application of FED to melting in aluminium and gold excited by intense femtosecond laser pulses will be discussed. The interplay of experiment and theory will be explored, particularly with respect to molecular dynamics simulations of the same processes we experimentally observe. Homogeneous nucleation emerges as an important melting mechanism under the strongly-driving conditions that we employ. Future applications of FED will be discussed in terms of progress to date. [ABSTRACT FROM AUTHOR]

Extended abstract of a paper presented at Microscopy and Microanalysis 2010 in Portland, Oregon, USA, August 1 – August 5, 2010. [ABSTRACT FROM PUBLISHER]

Solvated iron(II)-tris(bipyridine) ([FeII(bpy)3]2+) has been extensively studied with regard to the spin crossover (SCO) phenomenon. Herein, the ultrafast spin transition dynamics of single crystal [FeII(bpy)3](PF6)2 was characterized for the first time using femtosecond transient absorption (TA) spectroscopy. The single crystal environment is of interest for experiments that probe the nuclear motions involved in the SCO transition, such as femtosecond X-ray and electron diffraction. We found that the TA at early times is very similar to what has been reported in solvated [FeII(bpy)3]2+, whereas the later dynamics are perturbed in the crystal environment. The lifetime of the high-spin state is found to be much shorter (100 ps) than in solution due to chemical pressure exerted by the lattice. Oscillatory behavior was observed on both time scales. Our results show that single crystal [FeII(bpy)3](PF6)2 serves as an excellent model system for localized molecular spin transitions. [ABSTRACT FROM AUTHOR]

Correlated electron systems can undergo ultrafast photoinduced phase transitions involving concerted transformations of electronic and lattice structure. Understanding these phenomena requires identifying the key structural modes that couple to the electronic states.We report the ultrafast photoresponse of the molecular crystal Me4P[Pt(dmit)2]2, which exhibits a photoinduced charge transfer similar to transitions between thermally accessible states, and demonstrate how femtosecond electron diffraction can be applied to directly observe the associatedmolecularmotions. Even for such a complex system, the key large-amplitudemodes can be identified by eye and involve a dimer expansion and a librationalmode.The dynamics are consistent with the time-resolved optical study, revealing how the electronic, molecular, and lattice structures together facilitate ultrafast switching of the state. [ABSTRACT FROM AUTHOR]