Theoretical predictions show that depending on the populations of the Fe 3dxy, 3dxz, and 3dyz orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy)2]2+. The differences in the structure and molecular properties of these 5B2 and 5E quintets are very small and pose a substantial challenge for experiments to resolve them. Yet for a better understanding of the physics of this system, which can lead to the design of novel molecules with enhanced photoswitching performance, it is vital to determine which high-spin state is reached in the transitions that follow the light excitation. The quintet state can be prepared with a short laser pulse and can be studied with cutting-edge time-resolved X-ray techniques. Here we report on the application of an extended set of X-ray spectroscopy and scattering techniques applied to investigate the quintet state of [Fe(terpy)2]2+ 80 ps after light excitation. High-quality X-ray absorption, nonresonant emission, and resonant emission spectra as well as X-ray diffuse scattering data clearly reflect the formation of the high-spin state of the [Fe(terpy)2]2+ molecule; moreover, extended X-ray absorption fine structure spectroscopy resolves the Fe–ligand bond-length variations with unprecedented bond-length accuracy in time-resolved experiments. With ab initio calculations we determine why, in contrast to most related systems, one configurational mode is insufficient for the description of the low-spin (LS)–high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as 5E, in agreement with our theoretical expectations.

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Soluble methane monooxygenase (sMMO) is a multicomponent metalloenzyme that catalyzes the conversion of methane to methanol at ambient temperature using a nonheme, oxygen-bridged dinuclear iron cluster in the active site. Structural changes in the hydroxylase component (sMMOH) containing the diiron cluster caused by complex formation with a regulatory component (MMOB) and by iron reduction are important for the regulation of O2 activation and substrate hydroxylation. Structural studies of metalloenzymes using traditional synchrotron-based X-ray crystallography are often complicated by partial X-ray-induced photoreduction of the metal center, thereby obviating determination of the structure of the enzyme in pure oxidation states. Here, microcrystals of the sMMOH:MMOB complex from Methylosinus trichosporium OB3b were serially exposed to X-ray free electron laser (XFEL) pulses, where the ≤35 fs duration of exposure of an individual crystal yields diffraction data before photoreduction-induced structural changes can manifest. Merging diffraction patterns obtained from thousands of crystals generates radiation damage-free, 1.95 Å resolution crystal structures for the fully oxidized and fully reduced states of the sMMOH:MMOB complex for the first time. The results provide new insight into the manner by which the diiron cluster and the active site environment are reorganized by the regulatory protein component in order to enhance the steps of oxygen activation and methane oxidation. This study also emphasizes the value of XFEL and serial femtosecond crystallography (SFX) methods for investigating the structures of metalloenzymes with radiation sensitive metal active sites.

Nanostructures of transition metal oxides, such as zinc oxide, have attracted considerable interest for solar-energy conversion and photocatalysis. Both applications are sensitive to the transport and trapping of photoexcited charge carriers. The probing of electron trapping has recently become possible using time-resolved element-sensitive methods, such as X-ray spectroscopy. However, valence-band-trapped holes have so far escaped observation. Herein we use X-ray absorption spectroscopy combined with a dispersive X-ray emission spectrometer to probe the charge carrier relaxation and trapping processes in zinc oxide nanoparticles after above band-gap photoexcitation. Our results, supported by simulations, demonstrate that within 80 ps, photoexcited holes are trapped at singly charged oxygen vacancies, which causes an outward displacement by ~15% of the four surrounding zinc atoms away from the doubly charged vacancy. This identification of the hole traps provides insight for future developments of transition metal oxide-based nanodevices.

We employ few-femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy to reveal simultaneously the intra-and interband carrier relaxation and the light-induced structural dynamics in nanoscale thin films of layered 2H-MoTe2 semiconductor. By interrogating the valence electronic structure via localized Te 4d (39-46 eV) and Mo 4p (35-38 eV) core levels, the relaxation of the photoexcited hole distribution is directly observed in real time. We obtain hole thermalization and cooling times of 15±5 fs and 380±90 fs, respectively, and an electron-hole recombination time of 1.5±0.1 ps. Furthermore, excitations of coherent out-of-plane A1g (5.1 THz) and in-plane E1g (3.7 THz) lattice vibrations are visualized through oscillations in the XUV absorption spectra. By comparison to Bethe-Salpeter equation simulations, the spectral changes are mapped to real-space excited-state displacements of the lattice along the dominant A1g coordinate. By directly and simultaneously probing the excited carrier distribution dynamics and accompanying femtosecond lattice displacement in 2H-MoTe2 within a single experiment, our work provides a benchmark for understanding the interplay between electronic and structural dynamics in photoexcited nanomaterials.

Strong-field ionisation surprises with richness beyond current understanding despite decade long investigations. Ionisation with mid-IR light has promptly revealed unexpected kinetic energy structures that seem related to unanticipated quantum trajectories of the electrons. We measure first 3D momentum distributions in the deep tunneling regime (γ = 0.3) and observe surprising new electron dynamics of near-zero momentum electrons and extremely low momentum structures, below the eV, despite very high quiver energies of 95 eV. Such level of high-precision measurements at only 1 meV above the threshold, despite 5 orders higher ponderomotive energies, has now become possible with a specifically developed ultrafast mid-IR light source in combination with a reaction microscope, thereby permitting a new level of investigations into mid-IR recollision physics.

We study the structural dynamics of photoexcited ½CoðterpyÞ 2 2þ in an aqueous solution with ultrafast x-ray diffuse scattering experiments conducted at the Linac Coherent Light Source. Through direct comparisons with density functional theory calculations, our analysis shows that the photoexcitation event leads to elongation of the Co-N bonds, followed by coherent Co-N bond length oscillations arising from the impulsive excitation of a vibrational mode dominated by the symmetrical stretch of all six Co-N bonds. This mode has a period of 0.33 ps and decays on a subpicosecond time scale. We find that the equilibrium bond-elongated structure of the high spin state is established on a single-picosecond time scale and that this state has a lifetime of ∼7 ps. DOI: 10.1103/PhysRevLett.117.013002 Several Co(II) compounds are known to transition between their low spin (LS) and high spin (HS) electronic states [1][2][3]. Such transitions can be induced by temperature increase, excitation by light, or high magnetic fields [4], and they are accompanied by distinct changes in magnetic and structural properties that may be exploited in the design of display and memory devices [5,6] and in single-molecule spintronic applications [7]. The realization of exploitable spin-state transitions (SSTs) in Co(II) compounds is more challenging than in the corresponding Fe(II) complexes, which have been investigated in great detail during the last decades [8][9][10][11][12][13][14][15]. These challenges stem from the partial occupation of the antibonding e à g orbitals in the ground state, which leads to smaller structural changes arising from the SST phenomenon; the corresponding smaller energy barriers between the potential surfaces of the HS and LS Co(II) states result in faster dynamics [1], as well as a high sensitivity to the crystalline environment or to the solvent properties [2]. The key structural parameters for the SSTs are the Co-N bond lengths [8], but the time scales and the dynamics of the LS-HS transitions have remained unclear for Co compounds. Time-resolved x-ray scattering can be used to monitor such structural changes and dynamics if the time resolution of the experiment is sufficiently high. X-ray free electron lasers (XFELs) provide ultrashort (∼30 fs) x-ray pulses and high flux allowing the nuclear dynamics following photoexcitation to be recorded at the required femtosecond time scales [16,17]. Here, we report, for the first time, direct measurements of the excited-state structure and the ultrafast structural dynamics of a solvated Co(II) complex upon a photoinduced SST. Figure 1 shows the molecular structure of ½CoðterpyÞ 2 2þ ðterpy ¼ 2; 2 0 ∶6 0 ; 2 00 − terpyridineÞ. In this six-coordinated complex, the d 7 Co center can be either a LS doublet state or a HS quartet state [2,18]. In solid-state samples, the relative populations of both spin states depend strongly on the In this work, we utilized x-ray diffuse scattering (XDS) laser pump-x-ray probe experiments to study the formation, structure, and decay of...

Two-dimensional transition metal dichalcogenides (TMDs) draw strong interest in materials science, with applications in optoelectronics and many other fields. Good performance requires high carrier concentrations and long lifetimes. However, high concentrations accelerate energy exchange between charged particles by Auger-type processes, especially in TMDs where many-body interactions are strong, thus facilitating carrier trapping. We report time-resolved optical pump-THz probe measurements of carrier lifetimes as a function of carrier density. Surprisingly, the lifetime reduction with increased density is very weak. It decreases only by 20% when we increase the pump fluence 100 times. This unexpected feature of the Auger process is rationalized by our time-domain ab initio simulations. The simulations show that phonon-driven trapping competes successfully with the Auger process. On the one hand, trap states are relatively close to band edges, and phonons accommodate efficiently the electronic energy during the trapping. On the other hand, trap states localize around defects, and the overlap of trapped and free carriers is small, decreasing carrier–carrier interactions. At low carrier densities, phonons provide the main charge trapping mechanism, decreasing carrier lifetimes compared to defect-free samples. At high carrier densities, phonons suppress Auger processes and lower the dependence of the trapping rate on carrier density. Our results provide theoretical insights into the diverse roles played by phonons and Auger processes in TMDs and generate guidelines for defect engineering to improve device performance at high carrier densities.