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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.

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).

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.