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Stroboscopic visualization of nuclear or electron dynamics in atoms, molecules or solids requires ultrafast pump and probe pulses and a close to perfect synchronization between the two. We have developed a 3 MeV ultrafast electron diffraction (UED) probe technology that nominally reduces the electron bunch duration and the arrival time jitter to the subfemtosecond level. This simple configuration uses a radiofrequency photogun and a 90° achromatic bend and is designed to provide effectively jitter-free conditions. Terahertz streaking measurements reveal an electron bunch duration of 25 fs, even for a charge as high as 0.6 pC, and an arrival time jitter of 7.8 fs, the latter limited by only the measurement accuracy. From pump–probe measurements of photoexcited bismuth films, the instrument response function was determined to be 31 fs. This pioneering jitter-free technique paves the way towards UED of attosecond phenomena in atomic, molecular and solid-state dynamics. An ultrafast electron diffraction facility with an overall temporal resolution of 31 fs root mean square is developed. Even for a charge as high as 0.6 pC, the electron bunch duration and timing jitter are 25 fs and less than 10 fs, respectively.

We have developed a one-and-half -cell S-band radio-frequency (RF) photoelectron gun (photogun) fed by a coaxial coupler. The RF photogun is dedicated to ultrafast-electron-diffraction experiments by generating electron bunches of 3-MeV energy and a-few-pC charge, which is not strict condition compared to those for X-ray free-electron lasers. Brazing of RF cavities is welldeveloped process for making RF guns or RF accelerators. Sometimes, however, a failure occurs in the brazing process, causing the entire electron gun or accelerating cavity to spoil. Axial-symmetric design of the RF photogun permits indium sealing for cavity cells, a photocathode plate, and a coupling RF part. We firstly report that the indium-sealed RF photogun successfully meets the required performance and long-term stability for ultrafast electron diffraction experiments. We have stably operated the RF photogun for more than three years with the electron beam conditions of ~ 3-MeV energy, up-to-10-pC charge, and a repetition rate of 50 Hz. The quantum efficiency of the copper photocathode had improved from 10−6 to 10−5 depending on vacuum condition from 10−8 to 5 × 10−10 Torr, respectively. Measured emittance and energy spread of the generated electron beam showed 0.3 mm-mrad and less than 0.25%, respectively, for a bunch charge of ~ 2 pC, which agree well with those obtained by ASTRA simulation.

Nature / Physical science 582(7813), 520 - 524 (2020). doi:10.1038/s41586-020-2417-3, Fundamental studies of chemical reactions often consider the molecular dynamics along a reaction coordinate using a calculated or suggested potential energy surface1,2,3,4,5. But fully mapping such dynamics experimentally, by following all nuclear motions in a time-resolved manner���that is, the motions of wavepackets���is challenging and has not yet been realized even for the simple stereotypical bimolecular reaction6,7,8: A���B + C ��� A + B���C. Here we track the trajectories of these vibrational wavepackets during photoinduced bond formation of the gold trimer complex [Au(CN)2���]3 in an aqueous monomer solution, using femtosecond X-ray liquidography9,10,11,12 with X-ray free-electron lasers13,14. In the complex, which forms when three monomers A, B and C cluster together through non-covalent interactions15,16, the distance between A and B is shorter than that between B and C. Tracking the wavepacket in three-dimensional nuclear coordinates reveals that within the first 60 femtoseconds after photoexcitation, a covalent bond forms between A and B to give A���B + C. The second covalent bond, between B and C, subsequently forms within 360 femtoseconds to give a linear and covalently bonded trimer complex A���B���C. The trimer exhibits harmonic vibrations that we map and unambiguously assign to specific normal modes using only the experimental data. In principle, more intense X-rays could visualize the motion not only of highly scattering atoms such as gold but also of lighter atoms such as carbon and nitrogen, which will open the door to the direct tracking of the atomic motions involved in many chemical reactions., Published by Macmillan28177, London

With the recent successful development of X-ray free electron lasers (X-FELs), it became possible to explore sub-nano structure dynamics of materials with 100-fs temporal accuracy. Ultrafast electron diffraction (UED) can achieve similar performance at a much lower cost and on a smaller scale by using ultrashort and low-energy electron beams. The UEDs are suitable for studying thin films, surfaces, and gas samples that are difficult to study with the X-FELs. Starting from non-relativistic UEDs using low-energy electron beams of less than 100 keV, it led to the development of relativistic UEDs using a-few-MeV electron beams. These efforts have contributed to the identification of the unexplored mechanism of matter by observing the dynamics of atoms with higher temporal accuracy. Electron beam is easier to handle than X-rays, and various technologies are being developed to improve the performance of UED. We review UEDs historically based on the development of core technologies. And application researches with the UEDs will be outlined in this paper.

Intramolecular charge transfer (ICT) in a multibranched push–pull chromophore is a key photophysical process which is attracting attention due to its relevance to the development of highly efficient organic light-emitting diodes, but the excited-state dynamics of multibranched push–pull chromophores is still unclear. Here, using femtosecond transient absorption spectroscopy and singular value decomposition analysis, we studied the excited state dynamics of 2,6-bis(diphenylamino)anthraquinone (DPA-AQ-DPA), which contains two diphenylamino (DPA) groups as electron-donors (D) and anthraquinone (AQ) as an electron-acceptor (A) and is a candidate for an efficient red TADF (thermally activated delayed fluorescence) emitter. The emission of DPA-AQ-DPA exhibits large Stokes shifts with increasing solvent polarity, indicating that the emission can be attributed to an ICT process. The charge separated (CS) state formed by ICT undergoes torsional dynamics, involving twisting between D and A, resulting in the formati...

Time-resolved X-ray diffraction provides direct information on three-dimensional structures of reacting molecules and thus can be used to elucidate structural dynamics of chemical and biological reactions. In this review, we discuss time-resolved X-ray diffraction on small molecules and proteins with particular emphasis on its application to crystalline (crystallography) and liquid-solution (liquidography) samples. Time-resolved X-ray diffraction has been used to study picosecond and slower dynamics at synchrotrons and can now access even femtosecond dynamics with the recent arrival of X-ray free-electron lasers.

In this talk, we introduce the novel technique for real-time measurement of a ultrafast optical field by utilizing the relativistic electron beam. The direct electron-field interaction of our real-time oscilloscope guarantees the signal integrity of THz waveform measurement with a sampling rate of 75 Ts/s.

The experimental observation of femtosecond dynamics in atoms and molecules by stroboscopic technologies utilizing x ray or electron flashes has attracted much attention and has rapidly developed. We propose a feasible ultrafast electron diffraction (UED) technology with high brightness and a sub-10 fs temporal resolution. We previously demonstrated a UED system with an overall temporal resolution of 31 fs by using an RF photoelectron gun and a 90° achromatic bending structure. This UED structure enabled a bunch duration of 25 fs and a low timing jitter of less than 10 fs while maintaining a high bunch charge of 0.6 pC. In this paper, we demonstrate a simple way to further compress the electron bunch duration to sub-10 fs based on installing an energy filter in the dispersion section of the achromatic bend. The energy filter removes the electrons belonging to nonlinear parts of the phase space. Through numerical simulations, we demonstrate that the electron bunches can be compressed, at the sample position, to a 6.2 fs (rms) duration for a 100 fC charge. This result suggests that the energy filtering approach is more viable and effective than complicated beam-shaping techniques that commonly handle the nonlinear distribution of the electron beam. Furthermore, a gas-filled hollow core fiber compressor and a Ti:sapphire amplifier are used to implement pump laser pulses of less than 5 fs (rms). Thus, we could present the full simulation results of a sub-10 fs UED, and we believe that it will be one of the technical prototypes to challenge the sub-fs time resolution.

In this talk, we introduce our ultrashort electron accelerator facility and recent efforts for the THz-based temporal diagnostics of electron bunch. The THz-driven electron streak camera with a resolution of sub-10 femtoseconds is demonstrated by using the metallic split-ring resonator (SRR).

Determination of the optimum kinetic model is an essential prerequisite for characterizing dynamics and mechanism of a reaction. Here, we propose a simple method, termed as singular value decomposition-aided pseudo principal-component analysis (SAPPA), to facilitate determination of the optimum kinetic model from time-resolved data by bypassing any need to examine candidate kinetic models. We demonstrate the wide applicability of SAPPA by examining three different sets of experimental time-resolved data and show that SAPPA can efficiently determine the optimum kinetic model. In addition, the results of SAPPA for both time-resolved X-ray solution scattering (TRXSS) and transient absorption (TA) data of the same protein reveal that global structural changes of protein, which is probed by TRXSS, may occur more slowly than local structural changes around the chromophore, which is probed by TA spectroscopy. (C) 2017 Author(s).

Diiodomethane, CH2I2, in a polar solvent undergoes a unique photoinduced reaction whereby I2− and I3− are produced from its photodissociation, unlike for other iodine-containing haloalkanes. While previous studies proposed that homolysis, heterolysis, or solvolysis of iso-CH2I–I, which is a major intermediate of the photodissociation, can account for the formation of I2− and I3−, there has been no consensus on its mechanism and no clue for the reason why those negative ionic species are not observed in the photodissociation of other iodine-containing chemicals in the same polar solvent, for example, CHI3, C2H4I2, C2F4I2, I3−, and I2. Here, using time-resolved X-ray liquidography, we revisit the photodissociation mechanism of CH2I2 in methanol and determine the structures of all transient species and photoproducts involved in its photodissociation and reveal that I2− and I3− are formed via heterolysis of iso-CH2I–I in the photodissociation of CH2I2 in methanol. In addition, we demonstrate that the high polarity of iso-CH2I–I is responsible for the unique photochemistry of CH2I2.

The [Au(CN)2 (-)]3 trimer in water experiences a strong van der Waals interaction between the d(10) gold atoms due to large relativistic effect and can serve as an excellent model system to study the bond formation process in real time. The trimer in the ground state (S0) exists as a bent structure without the covalent bond between the gold atoms, and upon the laser excitation, one electron in the antibonding orbital goes to the bonding orbital, thereby inducing the formation of a covalent bond between gold atoms. This process has been studied by various time-resolved techniques, and most of the interpretation on the structure and dynamics converge except that the structure of the first intermediate (S1) has been debated due to different interpretations between femtosecond optical spectroscopy and femtosecond X-ray solution scattering. Recently, the excitation wavelength of 267 nm employed in our previous scattering experiment was suggested as the culprit for misinterpretation. Here, we revisited this issue by performing femtosecond X-ray solution scattering with 310 nm excitation and compared the results with our previous study employing 267 nm excitation. The data show that a linear S1 structure is formed within 500 fs regardless of excitation wavelength and the structural dynamics observed at both excitation wavelengths are identical to each other within experimental errors.

Characterization of transient molecular structures formed during chemical and biological processes is essential for understanding their mechanisms and functions. Over the last decade, time-resolved X-ray liquidography (TRXL) and time-resolved X-ray absorption spectroscopy (TRXAS) have emerged as powerful techniques for molecular and electronic structural analysis of photoinduced reactions in the solution phase. Both techniques make use of a pump–probe scheme that consists of (1) an optical pump pulse to initiate a photoinduced process and (2) an X-ray probe pulse to monitor changes in the molecular structure as a function of time delay between pump and probe pulses. TRXL is sensitive to changes in the global molecular structure and therefore can be used to elucidate structural changes of reacting solute molecules as well as the collective response of solvent molecules. On the other hand, TRXAS can be used to probe changes in both local geometrical and electronic structures of specific X-ray-absorbing atoms due to the element-specific nature of core-level transitions. These techniques are complementary to each other and a combination of the two methods will enhance the capability of accurately obtaining structural changes induced by photoexcitation. Here we review the principles of TRXL and TRXAS and present recent application examples of the two methods for studying chemical and biological processes in solution. Furthermore, we briefly discuss the prospect of using X-ray free electron lasers for the two techniques, which will allow us to keep track of structural dynamics on femtosecond time scales in various solution-phase molecular reactions.

Homodimeric hemoglobin (HbI) consisting of two subunits is a good model system for investigating the allosteric structural transition as it exhibits cooperativity in ligand binding. In this work, as an effort to extend our previous study on wild-type and F97Y mutant HbI, we investigate structural dynamics of a mutant HbI in solution to examine the role of well-organized interfacial water cluster, which has been known to mediate intersubunit communication in HbI. In the T72V mutant of HbI, the interfacial water cluster in the T state is perturbed due to the lack of Thr72, resulting in two less interfacial water molecules than in wild-type HbI. By performing picosecond time-resolved X-ray solution scattering experiment and kinetic analysis on the T72V mutant, we identify three structurally distinct intermediates (I1, I2, and I3) and show that the kinetics of the T72V mutant are well described by the same kinetic model used for wild-type and F97Y HbI, which involves biphasic kinetics, geminate recombination, and bimolecular CO recombination. The optimized kinetic model shows that the R-T transition and bimolecular CO recombination are faster in the T72V mutant than in the wild type. From structural analysis using species-associated difference scattering curves for the intermediates, we find that the T-like deoxy I3 intermediate in solution has a different structure from deoxy HbI in crystal. In addition, we extract detailed structural parameters of the intermediates such as E-F distance, intersubunit rotation angle, and heme-heme distance. By comparing the structures of protein intermediates in wild-type HbI and the T72V mutant, we reveal how the perturbation in the interfacial water cluster affects the kinetics and structures of reaction intermediates of HbI.