Fundamental studies of chemical reactions often consider the molecular dynamics along a reaction coordinate using a calculated or suggested potential energy surface
. 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 reaction
: 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)
in an aqueous monomer solution, using femtosecond X-ray liquidography
with X-ray free-electron lasers
. In the complex, which forms when three monomers A, B and C cluster together through non-covalent interactions
, 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.
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.
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.
Abstract
The deflection of charged particles is an intuitive way to visualize an electromagnetic oscillation of coherent light. Here, we present a real-time ultrafast oscilloscope for time-frozen ...visualization of a terahertz (THz) optical wave by probing light-driven motion of relativistic electrons. We found the unique condition of subwavelength metal slit waveguide for preserving the distortion-free optical waveform during its propagation. Momentary stamping of the wave, transversely travelling inside a metal slit, on an ultrashort wide electron bunch enables the single-shot recording of an ultrafast optical waveform. As a proof-of-concept experiment, we successfully demonstrated to capture the entire field oscillation of a THz pulse with a sampling rate of 75.7 TS/s. Owing to the use of transversely-wide and longitudinally-short electron bunch and transversely travelling wave, the proposed “single-shot oscilloscope” will open up new avenue for developing the real-time petahertz (PHz) metrology.
The structure of molecules, particularly the dynamic changes in structure, plays an essential role in understanding physical and chemical phenomena. Time-resolved (TR) scattering techniques serve as ...crucial experimental tools for studying structural dynamics, offering direct sensitivity to molecular structures through scattering signals. Over the past decade, the advent of x-ray free-electron lasers (XFELs) and mega-electron-volt ultrafast electron diffraction (MeV-UED) facilities has ushered TR scattering experiments into a new era, garnering significant attention. In this review, we delve into the basic principles of TR scattering experiments, especially focusing on those that employ x-rays and electrons. We highlight the variations in experimental conditions when employing x-rays vs electrons and discuss their complementarity. Additionally, cutting-edge XFELs and MeV-UED facilities for TR x-ray and electron scattering experiments and the experiments performed at those facilities are reviewed. As new facilities are constructed and existing ones undergo upgrades, the landscape for TR x-ray and electron scattering experiments is poised for further expansion. Through this review, we aim to facilitate the effective utilization of these emerging opportunities, assisting researchers in delving deeper into the intricate dynamics of molecular structures.
Time-resolved X-ray liquidography (TRXL) has emerged as a powerful technique for studying the structural dynamics of small molecules and macromolecules in liquid solutions. However, TRXL has limited ...sensitivity for small molecules containing light atoms only, whose signal has lower contrast compared with the signal from solvent molecules. Here, we present an alternative approach to bypass this limitation by detecting the change in solvent temperature resulting from a photoinduced reaction. Specifically, we analyzed the heat dynamics of TRXL data obtained from p-hydroxyphenacyl diethyl phosphate (HPDP). This analysis enabled us to experimentally determine the number of intermediates and their respective enthalpy changes, which can be compared to theoretical enthalpies to identify the intermediates. This work demonstrates that TRXL can be used to uncover the kinetics and reaction pathways for small molecules without heavy atoms even if the scattering signal from the solute molecules is buried under the strong solvent scattering signal.
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.
TRXL and TRXAS are powerful techniques for real-time probing of structural and electronic dynamics of photoinduced reactions in solution phase.
Ultrafast electron diffraction (UED) has evolved to be a powerful tool for the study of structural dynamics with subpicosecond temporal resolution and subatomic spatial resolution. Recently, there ...have been intense research efforts toward femtosecond timing jitter and stability for improving the temporal resolution of UEDs, however, so far there has been no work showing long‐term (e.g., >1 h) stable timing for MeV‐level UED systems. In this article, a comprehensive timing synchronization method, based on optical‐radiofrequency synchronization and THz streaking, is demonstrated to maintain sub‐10‐fs long‐term timing stability for radiofrequency‐gun‐based MeV‐level UED, which results in 5.5 fs root‐mean‐square timing drift maintained over 4600 s. With high electron energy and low timing drift, the demonstrated capability is an important step toward studying ultrafast phenomena in samples with low scattering power, such as volatile gases and 2D materials.
A THz‐streaking based timing system with sub‐10‐fs stability is implemented to operate MeV‐class ultrafast electron diffraction apparatus. Various timing methodologies, such as radiofrequency‐to‐laser synchronization, optical timing monitoring, electron dispersion control, are applied to enable THz‐streaking with few femtosecond resolution. With the THz‐driven streak camera, timing of ultrafast electron bunch is stabilized to 5.5 fs in rms.
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.
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.
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