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The photoinduced switching of Fe(II)-based spin-crossover complexes from singlet to quintet takes place at ultrafast time scales. This a priori spin-forbidden transition triggered numerous time-resolved experiments of solvated samples to elucidate the mechanism at play. The involved intermediate states remain uncertain. We apply ultrafast x-ray spectroscopy in molecular films as a method sensitive to spin, electronic, and nuclear degrees of freedom. Combining the progress in molecule synthesis and film growth with the opportunities at x-ray free-electron lasers, we analyze the transient evolution of the Fe L3 fine structure at room temperature. Our measurements and calculations indicate the involvement of an Fe triplet intermediate state. The high-spin state saturates at half of the available molecules, limited by molecule-molecule interaction within the film.

Hydrogen bonding is essential in electron transfer processes at water-electrode interfaces. We study the impact of the H-bonding of water as a solvent molecule on real-time electron transfer dynamics across a Cs+-Cu(111) ion-metal interface using femtosecond time-resolved two-photon photoelectron spectroscopy. We distinguish in the formed water-alkali aggregates two regimes below and above two water molecules per ion. Upon crossing the boundary of these regimes, the lifetime of the excess electron localized transiently at the Cs+ ion increases from 40 to 60 femtoseconds, which indicates a reduced alkali-metal interaction. Furthermore, the energy transferred to a dynamic structural rearrangement due to hydration is reduced from 0.3 to 0.2 eV concomitantly. These effects are a consequence of H-bonding and the beginning formation of a nanoscale water network. This finding is supported by real-space imaging of the solvatomers and vibrational frequency shifts of the OH stretch and bending modes calculated for these specific interfaces., Comment: 8 pages, 5 figures

Understanding the microscopic spatio-temporal dynamics of nonequilibrium charge carriers in heterosystems promises optimization of process and device design towards desired energy transfer. Hot electron transport is governed by scattering with other electrons, defects, and bosonic excitations. Analysis of the energy dependence of scattering pathways and identification of diffusive, super-diffusive, and ballistic transport regimes are current challenges. We determine in femtosecond time-resolved two-photon photoelectron emission spectroscopy the energy-dependent change of the electron propagation time through epitaxial Au/Fe(001) heteostructures as a function of Au layer thickness for energies of 0.5 to \unit[2.0]{eV} above the Fermi energy. We describe the laser-induced nonequilibrium electron excitation and injection across the Fe/Au interface using real-time time-dependent density functional theory and analyze the electron propagation through the Au layer by microscopic electron transport simulations. We identify ballistic transport of minority electrons at energies with a nascent, optically excited electron population which is determined by the combination of photon energy and the specific electronic structure of the material. At lower energy, super-diffusive transport with 1 to 4 scattering events dominates. The effective electron velocity accelerates from 0.3 to \unit[1]{nm/fs} with an increase in the Au layer thickness from 10 to 100~nm. This phenomenon is explained by electron transport that becomes preferentially aligned with the interface normal for thicker Au layers, which facilitates electron momentum / energy selection by choice of the propagation layer thickness.

Photo-doped states in strongly correlated charge transfer insulators are characterized by $d$-$d$ and $d$-$p$ interactions and the resulting intertwined dynamics of charge excitations and local multiplets. Here we use femtosecond x-ray absorption spectroscopy in combination with dynamical mean-field theory to disentangle these contributions in NiO. Upon resonant optical excitation across the charge transfer gap, the Ni $L_3$ and O $K$ absorption edges red-shift for $>10$ ps, associated with photo-induced changes in the screening environment. An additional signature below the Ni $L_3$ edge is identified for $<1$ ps, reflecting a transient nonthermal population of local many-body multiplets. We employ a nonthermal generalization of the multiplet ligand field theory to show that the feature originates from $d$-$d$ transitions. Overall, the photo-doped state differs significantly from a chemically doped state. Our results demonstrate the ability to reveal excitation pathways in correlated materials by x-ray spectroscopies, which is relevant for ultrafast materials design.

Understanding heterogeneous charge transfer is crucial if we are to build the best electrolyzers, fuel cells and photoelectrochemical water splitting devices that chemistry allows. Because the elementary processes involved have timescales ranging from femto- to milliseconds, direct simulation is not generally possible. Model Hamiltonian approaches thus have a crucial role in gaining mechanistic insight. Current generations of such theories describe a reactant(s) or product(s) that interacts with electrolyte via a single effective interaction. Such approaches thus obscure the extent to which particular solvent fluctuations influence charge transfer. Here we demonstrate experimentally that for a prototypical system, a ferrocene terminated alkane thiol self-assembled monolayer (SAM) on gold in contact with aqueous electrolyte, charge transfer from the Au to the ferrocene can be induced by vibrational excitation of the ferrocene aromatic CH. Intriguingly the energy of the aromatic CH vibration, 0.38 eV, is a large fraction of the effective solvent interaction strength inferred for the ferrocene/ferrocenium system in prior electrochemical studies: 0.85 eV. Our results thus demonstrate the coupling of charge transfer to a specific solvent motion and more generally imply that solvent may affect reduction/oxidation rates in electrocatalysis by coupling to a few distinct solvent motions. Identifying these motions is crucial in rationalizing trends in reactivity with change in electrolyte and thus in pursuing electrolyte engineering from first principles., Comment: 18 pages, 6 figures

The transport of optically excited, hot electrons in heterostructures is analyzed by femtosecond, time-resolved two-photon photoelectron emission spectroscopy (2PPE) for epitaxial Au/Fe/MgO(001). We compare the temporal evolution of the 2PPE intensity upon optically pumping Fe or Au, while the probing occurs on the Au surface. In the case of Fe-side pumping, assuming independent relaxation in the Fe and Au layers, we determine the hot electron relaxation times in these individual layers by an analysis of the Au layer thickness dependence of the observed, effective electron lifetimes in the heterostructure. We show in addition that such a systematic analysis fails for the case of Au-side pumping due to the spatially distributed optical excitation density, which varies with the Au layer thickness. This work extends a previous study [Beyazit et al., Phys. Rev. Lett. 125, 076803 (2020)] by new data leading to reduced error bars in the determined lifetimes and by a non-linear term in the Au-thickness dependent data analysis which contributes for similar Fe and Au film thicknesses., Comment: 8 pages, 6 figures

The pulse intensity from X-ray free-electron lasers (FELs) can create extreme excitation densities in solids, entering the regime of non-linear X-ray-matter interactions. We show L3-edge absorption spectra of metallic nickel thin films with fluences entering a regime where several X-ray photons are incident per absorption cross-section. Main features of the observed non-linear spectral changes are described with a predictive rate model for electron population dynamics during the pulse, utilizing a fixed density of states and tabulated ground-state properties., Comment: The main text contains 5 pages and 4 figures, the total length including supplement is 14 pages, 7 figures and one table. See also the simultaneously submitted paper about the rate model

Femtosecond transient soft X-ray Absorption Spectroscopy (XAS) is a very promising technique that can be employed at X-ray Free Electron Lasers (FELs) to investigate out-of-equilibrium dynamics for material and energy research. Here we present a dedicated setup for soft X-rays available at the Spectroscopy & Coherent Scattering (SCS) instrument at the European X-ray Free Electron Laser (EuXFEL). It consists of a beam-splitting off-axis zone plate (BOZ) used in transmission to create three copies of the incoming beam, which are used to measure the transmitted intensity through the excited and unexcited sample, as well as to monitor the incoming intensity. Since these three intensity signals are detected shot-by-shot and simultaneously, this setup allows normalized shot-by-shot analysis of the transmission. For photon detection, the DSSC imaging detector, which is capable of recording up to 800 images at 4.5 MHz frame rate during the FEL burst, is employed and allows approaching the photon shot-noise limit. We review the setup and its capabilities, as well as the online and offline analysis tools provided to users., Comment: 11 figures

The complex electronic structure of metallic ferromagnets is determined by a balance between exchange interaction, electron hopping leading to band formation, and local Coulomb repulsion. The interplay between the respective terms of the Hamiltonian is of fundamental interest, since it produces most, if not all, of the exotic phenomena observed in the solid state. By combining high energy and temporal resolution in femtosecond time-resolved X-ray absorption spectroscopy with ab initio time-dependent density functional theory we analyze the electronic structure in fcc Ni on the time scale of these interactions in a pump-probe experiment. We distinguish transient broadening and energy shifts in the absorption spectra, which we demonstrate to be caused by electron repopulation and correlation-induced modifications of the electronic structure, respectively. Importantly, the theoretical description of this experimental result hence requires to take the local Coulomb interaction into account, revealing a temporal interplay between band formation, exchange interaction, and Coulomb repulsion.

Understanding the molecular and electronic structure of electrolytes at interfaces requires an analysis of the interactions between the electrode surface, the ions, and the solvent environment on equal footing. Here, we tackle this challenge by exploring the initial stages of Cs+ hydration on a Cu(111) surface by combining experiment and theory. Remarkably, we observe "inside out" solvation of Cs ions, i.e, their preferential location at the perimeter of the water clusters on the metal surface. In addition, water-Cs complexes containing multiple Cs+ ions are observed to form at these surfaces. Established models based on maximum ion-water coordination and the double layer notion cannot account for this situation and the complex interplay of microscopic interactions is the key to a fundamental understanding., Comment: 5 pages, 3 figures

In condensed matter, scattering processes determine the transport of charge carriers. In case of heterostructures, interfaces determine many dynamic properties like charge transfer and transport and spin current dynamics. Here we discuss optically excited electron dynamics and their propagation across a lattice-matched, metal-metal interface of single crystal quality. Using femtosecond time-resolved linear photoelectron spectroscopy upon optically pumping different constituents of the heterostructure we establish a technique which probes the electron propagation and its energy relaxation simultaneously. In our approach a near-infrared pump pulse excites electrons directly either in the Au layer or in the Fe layer of epitaxial Au/Fe/MgO(001) heterostructures while the transient photoemission spectrum is measured by an ultraviolet probe pulse on the Au surface. Upon femtosecond laser excitation, we analyze the relative changes in the electron distribution close to the Fermi energy and assign characteristic features of the time-dependent electron distribution to transport of hot and non-thermalized electrons from the Fe layer to the Au surface and vice versa. From the measured transient electron distribution we determine the excess energy which we compare with a calculation based on the two-temperature model and takes diffusive electron transport into account. On this basis we identify a transition from a super-diffusive to a diffusive transport regime to occur for a Au layer thickness of 20-30~nm., Comment: 9 pages, 7 figures, submitted to Physical Review Research

The equilibration of electronic carriers in metals after excitation by an ultra-short laser pulse provides an important class of non-equilibrium phenomena in metals and allows measuring the effective electron-phonon coupling parameter. Since the observed decay of the electronic distribution is governed by the interplay of both electron-electron and electron-phonon scattering, the interpretation of experimental data must rely on models that ideally should be easy to handle, yet accurate. In this work, an extended rate-equation model is proposed that explicitly includes non-thermal electronic carriers while at the same time incorporating data from first-principles calculations of the electron-phonon coupling via Eliashberg-Migdal theory. The model is verified against experimental data for thin Pb films grown on Si(111). Improved agreement between theory and experiment at short times (<0.3ps) due to non-thermal electron contributions is found. Moreover, the rate equations allow for widely different coupling strength to different phonon subsystems. Consequently, an indirect, electron-mediated energy transfer between strongly and weakly coupled groups of phonons can be observed in the simulations that leads to a retarded equilibration of the subsystems only after several picoseconds., Comment: 11 pages, 6 figures

Employing femtosecond laser pulses in front and back side pumping of Au/Fe/MgO(001) combined with detection in two-photon photoelectron emission spectroscopy we analyze local relaxation dynamics of excited electrons in buried Fe, injection into Au across the Fe-Au interface, and electron transport across the Au layer at 0.6 to 2.0 eV above the Fermi energy. By analysis as a function of Au film thickness we obtain the electron lifetimes of bulk Au and Fe and distinguish the relaxation in the heterostructure's constituents. We also show that the excited electrons propagate through Au in a superdiffusive regime and conclude further that electron injection across the epitaxial interface proceeds ballistically by electron wavepacket propagation., Comment: 5 pages, 4 figures

We determine the impact of electron solvation on D$_2$O structures adsorbed on Cu(111) with low temperature scanning tunneling microscopy, two-photon photoemission, and ab initio theory. UV photons generating solvated electrons lead not only to transient, but also to permanent structural changes through the rearrangement of individual molecules. The persistent changes occur near sites with a high density of dangling OH groups that facilitate electron solvation. We conclude that energy dissipation during solvation triggers permanent molecular rearrangement via vibrational excitation.

High-energy femtosecond laser pulses in the mid-infrared (MIR) wavelength range are essential for a wide range of applications from strong-field physics to selectively pump and probe low energy excitations in condensed matter and molecular vibrations. Here we report a four stage optical parametric chirped pulse amplifier (OPCPA) which generates ultrashort pulses at a central wavelength of 3000 nm with 430 $\mu$J energy per pulse at a bandwidth of 490 nm. Broadband emission of a Ti:sapphire oscillator seeds synchronously the four OPCPA stages at 800 nm and the pump line at 1030 nm. The first stage amplifies the 800 nm pulses in BBO using a non-collinear configuration. The second stage converts the wavelength to 1560 nm using difference frequency generation in BBO in a collinear geometry. The third stage amplifies this idler frequency non-collinearly in KTA. Finally, the fourth stage generates the 3000 nm radiation in a collinear configuration in LiIO$_3$ due the broad amplification bandwidth this crystal provides. We compress these pulses to 65 fs by transmission through sapphire. Quantitative calculations of the individual non-linear processes in all stages verify that our OPCPA architecture operates close to optimum efficiency at minimum absorption losses, which suggests that this particular design is very suitable for operation a high average power at multi kHz repetition rates., Comment: 6 figures

Employing time-resolved photoelectron spectroscopy we analyze the relaxation dynamics of hot electrons in the charge density wave / Mott material 1T-TaS_2. At 1.2 eV above the Fermi level we observe a hot electron lifetime of 12 +- 5 fs in the metallic state and of 60 +- 10 fs in the broken symmetry ground state - a direct consequence of the reduced phase space for electron-electron scattering determined by the Mott gap. Boltzmann equation calculations which account for the interaction of hot electrons in a Bloch band with a doublon-holon excitation in the Mott state provide insight into the unoccupied electronic structure in the correlated state., Comment: 6 pages, 3 figures

Strongly correlated systems exhibit intriguing properties caused by intertwined microscopic in- teractions that are hard to disentangle in equilibrium. Employing non-equilibrium time-resolved photoemission spectroscopy on the quasi-two-dimensional transition-metal dichalcogenide 1T-TaS$_2$, we identify a spectroscopic signature of double occupied sites (doublons) that are reflects fundamental Mott physics. Doublon-hole recombination is estimated to occur on time scales of one electronic hopping cycle $\hbar/J\approx$ 14 fs. Despite strong electron-phonon coupling the dynamics can be explained by purely electronic effects captured by the single band Hubbard model, where thermalization is fast in the small-gap regime. Qualitative agreement with the experimental results however requires the assumption of an intrinsic hole-doping. The sensitivity of the doublon dynamics on the doping level provides a way to control ultrafast processes in such strongly correlated materials.

We analyze laser-induced ultrafast, spatially inhomogeneous magnetization dynamics of epitaxial Co/Cu(001) films in a 0.4-10 nm thickness range with time-resolved magnetization-induced second harmonic generation, which probes femtosecond spin dynamics at the vacuum/Co and Co/Cu interfaces. The interference of these two contributions makes the overall signal particularly sensitive to differences in the transient magnetization redistribution between the two interfaces, i.e. ultrafast magnetization profiles in the ferromagnetic film. We find in films of up to 3 nm thickness a stronger demagnetization at the surface, because the film thickness is smaller than the effective mean free path of the spin current mediating the demagnetization, i.e. the difference between the mean free paths of the majority and minority carriers. For film thicknesses larger than 3 nm, the magnetization profile reverses, since majority spins can escape into the conducting substrate only from the interface-near region., Comment: 4 pages, 4 figures

Using the sensitivity of magneto-induced second harmonic generation to spin currents (SC), we demonstrate in Fe/Au/Fe/MgO(001) pseudo spin valves the generation of 250 fs-long SC pulses. Their temporal profile indicates that superdiffusive hot electron transport across a sub-100~nm Au layer is close to the ballistic limit and the pulse duration is primarily determined by the thermalization time of laser-excited hot carriers in Fe. Considering the calculated spin-dependent Fe/Au interface transmittance we conclude that a non-thermal spin-dependent Seebeck effect is responsible for the generation of ultrashort SC pulses. We also show that hot electron spins rotate upon interaction with non-collinear magnetization at the Au/Fe interface, which holds high potential for future spintronic devices., Comment: 5 pages, 4 figures

Spintronics had a widespread impact over the past decades due to transferring information by spin rather than electric currents. Its further development requires miniaturization and reduction of characteristic timescales of spin dynamics combining the sub-nanometer spatial and femtosecond temporal ranges. These demands shift the focus of interest towards the fundamental open question of the interaction of femtosecond spin current (SC) pulses with a ferromagnet (FM). The spatio-temporal properties of the impulsive spin transfer torque exerted by ultrashort SC pulses on the FM open the time domain for probing non-uniform magnetization dynamics. Here we employ laser-generated ultrashort SC pulses for driving ultrafast spin dynamics in FM and analyzing its transient local source. Transverse spins injected into FM excite inhomogeneous high-frequency spin dynamics up to 0.6 THz, indicating that the perturbation of the FM magnetization is confined to 2 nm., Comment: 6 pages, 4 figures. Supplementary Information: 5 pages, 4 figures

We study the Fermi-Hubbard model in the strongly correlated Mott phase under the influence of a harmonically oscillating electric field, e.g., a pump laser. In the Peierls representation, this pump field can be represented as an oscillating phase of the hopping rate $J(t)$, such that the effective time-averaged rate $\bar J$ is reduced, i.e., switching the pump laser suddenly is analogous to a quantum quench. Apart from this time-averaged rate $\bar J$, it is well known that the oscillating component of $J(t)$ can resonantly create particle-hole pairs if the pump frequency $\omega_{\rm pump}$ equals (or a little exceeds) the Mott gap. In addition, we find that it is possible to create multiple pairs if $\omega_{\rm pump}$ is near an integer multiple of the gap. These findings should be relevant for pump-probe experiments.

A major challenge in understanding the cuprate superconductors is to clarify the nature of the fundamental electronic correlations that lead to the pseudogap phenomenon. Here we use ultrashort light pulses to prepare a non-thermal distribution of excitations and capture novel properties that are hidden at equilibrium. Using a broadband (0.5-2 eV) probe we are able to track the dynamics of the dielectric function, unveiling an anomalous decrease of the scattering rate of the charge carriers in a pseudogap-like region of the temperature ($T$) and hole-doping ($p$) phase diagram. In this region, delimited by a well-defined $T^*_{neq}(p)$ line, the photo-excitation process triggers the evolution of antinodal excitations from gapped (localized) to delocalized quasi-particles characterized by a longer lifetime. The novel concept of photo-enhanced antinodal conductivity is naturally explained within the single-band Hubbard model, in which the short-range Coulomb repulsion leads to a k-space differentiation between "nodal" quasiparticles and antinodal excitations., Comment: accepted for publication on Nature Communications

We employed femtosecond time- and angle-resolved photoelectron spectroscopy to analyze the response of the electronic structure of the 122 Fe-pnictide parent compounds Ba/EuFe_2As_2 and optimally doped BaFe_{1.85}Co_{0.15}As_2 near the \Gamma point to femtosecond optical excitation. We identify pronounced changes of the electron population within several 100 meV above and below the Fermi level, which we explain as combination of (i) coherent lattice vibrations, (ii) a hot electron and hole distribution, and (iii) transient modifications of the chemical potential. The response of the three different materials is very similar. In the Fourier transformation of the time-dependent photoemission intensity we identify three modes at 5.6, 3.3, and 2.6 THz. While the highest frequency mode is safely assigned to the A_{1g} mode, the other two modes require a discussion in comparison to literature. The time-dependent evolution of the hot electron distribution follows a simplified description of a transient three temperature model which considers two heat baths of lattice vibrations, which are more weakly and strongly coupled to transiently excited electron population. Still the energy transfer from electrons to the strongly coupled phonons results in a rather weak, momentum-averaged electron-phonon coupling quantified by values for \lambda<\omega^2> between 30 and 70 meV^2. The chemical potential is found to present a transient modulation induced by the coherent phonons. This change in the chemical potential is particularly strong in a two band system like in the 122 Fe-pnictide compounds investigated here due to the pronounced variation of the electrons density of states close to the equilibrium chemical potential., Comment: 10 pages, 6 figures

A time domain approach to probe hot carrier-induced spin dynamics is demonstrated. The experiments are performed in epitaxial Au/Fe/MgO(001), where spin-polarized hot carriers are excited in the Fe layer by 35 fs laser pulses. They propagate to the Au surface where the transient spin polarization is detected by magneto-induced second harmonic generation. Different energies of majority and minority hot carriers excited in the exchange-split Fe band structure lead to their spindependent lifetimes in Au. Accordingly, two spin-polarized current contributions which propagate superdiffusively at different velocities result in a spin current pulse of about 100 fs duration., Comment: 5 pages, 4 figures

Ultrafast laser-induced demagnetization of Gd(0001) has been investigated by magneto-induced optical second harmonic generation and the magneto-optical Kerr effect which facilitate a comparison of surface and bulk dynamics. We observe pronounced differences in the transient changes of the surface and bulk sensitive magneto-optical signals which we attribute to transfer of optically excited, spin-polarized carriers between surface and bulk states of the Gd(0001) film. A fluence dependent analysis of the bulk magnetization dynamics results in a weak variation of the demagnetization time constant, which starts at about 700 fs and increases by 10% within a fluence variation up to 1 mJ/cm2. We compare these results with fluence dependent changes in the transient energy density calculated by the two temperature model. The determined characteristic times of excess energy transfer from the electron system to the lattice, which is mediated by e-ph scattering, range from 0.2 - 0.6 ps. Such a more pronounced fluence dependent change in the characteristic time compared to the observed rather weakly varying demagnetization times suggests a more advanced description of the optically excited state than by the two-temperature model., Comment: 15 pages, 4 figures

Due to an error this article has been annouced as a new article instead of a corrected version of article 1010.1374., Comment: This paper has been withdrawn