Crystalline systems consisting of small-molecule building blocks have emerged as promising materials with diverse applications. It is of great importance to characterize not only their static structures but also the conversion of their structures in response to external stimuli. Femtosecond time-resolved crystallography has the potential to probe the real-time dynamics of structural transitions, but, thus far, this has not been realized for chemical reactions in non-biological crystals. In this study, we applied time-resolved serial femtosecond crystallography (TR-SFX), a powerful technique for visualizing protein structural dynamics, to a metal–organic framework, consisting of Fe porphyrins and hexazirconium nodes, and elucidated its structural dynamics. The time-resolved electron density maps derived from the TR-SFX data unveil trifurcating structural pathways: coherent oscillatory movements of Zr and Fe atoms, a transient structure with the Fe porphyrins and Zr₆ nodes undergoing doming and disordering movements, respectively, and a vibrationally hot structure with isotropic structural disorder. These findings demonstrate the feasibility of using TR-SFX to study chemical systems.

The X-ray free-electron laser of the Pohang Accelerator Laboratory (PAL-XFEL) was opened to users in 2017. Since then, significant progress has been made in PAL-XFEL operation and beamline experiments. This includes increasing the FEL pulse energy, increasing the FEL photon energy, generating self-seeding FEL, and trials of two-color operation. In the beamline, new instruments or endstations have been added or are being prepared. Overall, beamline operation has been stabilized since its initiation, which has enabled excellent scientific results through efficient user experiments. In this paper, we describe details of the recent progress of the PAL-XFEL.

The search for the liquid-liquid critical point in supercooled water is challenging owing to rapid crystallization. We studied supercooled water at timescales before ice formation by heating high- and low-density amorphous ices using infrared ultrafast laser pulses, followed by x-ray scattering. By varying the pump laser fluence, we accessed liquid states straddling the predicted critical point. We observed a crossover from a discontinuous to a continuous transition at which broad and slow structural variations occurred, consistent with critical fluctuations and slowing down. We also observed a rapid increase in the heat capacity indicating a critical divergence at 210 ± 8 K coincident with enhanced density fluctuations. These results suggest that our experiments have directly probed the vicinity of a critical point in supercooled water.

Understanding the ultrafast dynamics of molecules is of fundamental importance. Time-resolved X-ray absorption spectroscopy (TR-XAS) is a powerful spectroscopic technique for unveiling the time-dependent structural and electronic information of molecules that has been widely applied in various fields. Herein, the design and technical achievement of a newly developed experimental apparatus for TR-XAS measurements in the tender X-ray range with X-ray free-electron lasers (XFELs) at the Pohang Accelerator Laboratory XFEL (PAL-XFEL) are described. Femtosecond TR-XAS measurements were conducted at the Ru L ₃-edge of well known photosensitizer tris(bipyridine)ruthenium(II) chloride ([Ru(bpy)₃]²⁺) in water. The results indicate ultrafast photoinduced electron transfer from the Ru center to the ligand, which demonstrates that the newly designed setup is applicable for monitoring ultrafast reactions in the femtosecond domain.

The direct observation of the structure of micrometer-sized vapor-deposited ice is performed at Pohang Accelerator Laboratory x-ray free electron laser (PAL-XFEL). The formation of micrometer-sized ice crystals and their structure is important in various fields, including atmospheric science, cryobiology, and astrophysics, but understanding the structure of micrometer-sized ice crystals remains challenging due to the lack of direct observation. Using intense x-ray diffraction from PAL-XFEL, we could observe the structure of micrometer-sized vapor-deposited ice below 150 K with a thickness of 2–50 μm grown in an ultrahigh vacuum chamber. The structure of the ice grown comprises cubic and hexagonal sequences that are randomly arranged to produce a stacking-disordered ice. We observed that ice with a high cubicity of more than 80% was transformed to partially oriented hexagonal ice when the thickness of the ice deposition grew beyond 5 μm. This suggests that precise temperature control and clean deposition conditions allow μm-thick ice films with high cubicity to be grown on hydrophilic Si3N4 membranes. The low influence of impurities could enable in situ diffraction experiments of ice nucleation and growth from interfacial layers to bulk ice.

Time-resolved x-ray liquidography (TRXL) is a powerful technique for directly tracking ultrafast structural dynamics in real space. However, resolving the motion of vibrational wavepackets generated by femtosecond laser pulses remains challenging due to the limited temporal resolution and signal-to-noise ratio (SNR) of experimental data. This study addresses these challenges by introducing singular spectrum analysis (SSA) as an efficient method for extracting oscillatory signals associated with vibrational wavepackets from TRXL data. To evaluate its performance, we conducted a comparative study using simulated TRXL data, demonstrating that SSA outperforms conventional analysis methods such as the Fourier transform of temporal profiles and singular value decomposition, particularly under low SNR conditions. We further applied SSA to experimental TRXL data on the photodissociation of triiodide (I3−) in methanol, successfully isolating oscillatory signals arising from wavepacket dynamics in ground-state I3− and excited-state I2−, which had been challenging to resolve in previous TRXL studies. These results establish SSA as a highly effective tool for analyzing ultrafast structural dynamics in time-resolved experiments and open new opportunities for studying wavepacket dynamics in a wide range of photoinduced reactions.