Spin-State Transition and Metal-Insulator Transition in La1−x_{1-x}Eux_xCoO3_3}

We present a study of the structure, the electric resistivity, the magnetic susceptibility, and the thermal expansion of La$_{1-x}$Eu$_x$CoO$_3$. LaCoO$_3$ shows a temperature-induced spin-state transition around 100 K and a metal-insulator transition around 500 K. Partial substitution of La$^{3+}$ by the smaller Eu$^{3+}$ causes chemical pressure and leads to a drastic increase of the spin gap from about 190 K in LaCoO$_3$ to about 2000 K in EuCoO$_3$, so that the spin-state transition is shifted to much higher temperatures. A combined analysis of thermal expansion and susceptibility gives evidence that the spin-state transition has to be attributed to a population of an intermediate-spin state with orbital order for $x<0.5$ and without orbital order for larger $x$. In contrast to the spin-state transition, the metal-insulator transition is shifted only moderately to higher temperatures with increasing Eu content, showing that the metal-insulator transition occurs independently from the spin-state distribution of the Co$^{3+}$ ions. Around the metal-insulator transition the magnetic susceptibility shows a similar increase for all $x$ and approaches a doping-independent value around 1000 K indicating that well above the metal-insulator transition the same spin state is approached for all $x$.Comment: 10 pages, 6 figure

Epitaxial and layer-by-layer growth of EuO thin films on yttria-stabilized cubic zirconia (001) using MBE distillation

We have succeeded in growing epitaxial and highly stoichiometric films of EuO on yttria-stabilized cubic zirconia (YSZ) (001). The use of the Eu-distillation process during the molecular beam epitaxy assisted growth enables the consistent achievement of stoichiometry. We have also succeeded in growing the films in a layer-by-layer fashion by fine tuning the Eu vs. oxygen deposition rates. The initial stages of growth involve the limited supply of oxygen from the YSZ substrate, but the EuO stoichiometry can still be well maintained. The films grown were sufficiently smooth so that the capping with a thin layer of aluminum was leak tight and enabled ex situ experiments free from trivalent Eu species. The findings were used to obtain recipes for better epitaxial growth of EuO on MgO (001).Comment: 10 pages, 15 figure

Epitaxy, stoichiometry, and magnetic properties of Gd-doped EuO films on YSZ (001)

We have succeeded in preparing high-quality Gd-doped single-crystalline EuO films. Using Eu-distillation-assisted molecular beam epitaxy and a systematic variation in the Gd and oxygen deposition rates, we have been able to observe sustained layer-by-layer epitaxial growth on yttria-stabilized cubic zirconia (001). The presence of Gd helps to stabilize the layer-by-layer growth mode. We used soft x-ray absorption spectroscopy at the Eu and Gd M4,5 edges to confirm the absence of Eu3+ contaminants and to determine the actual Gd concentration. The distillation process ensures the absence of oxygen vacancies in the films. From magnetization measurements we found the Curie temperature to increase smoothly as a function of doping from 70 K up to a maximum of 125 K. A threshold behavior was not observed for concentrations as low as 0.2%.Comment: 8 pages, 9 figure

Charge transfer in dissociating iodomethane and fluoromethane molecules ionized by intense femtosecond X-ray pulses

Citation: Boll, R., Erk, B., Coffee, R., Trippel, S., Kierspel, T., Bomme, C., . . . Rudenko, A. (2016). Charge transfer in dissociating iodomethane and fluoromethane molecules ionized by intense femtosecond X-ray pulses. Structural Dynamics, 3(4). doi:10.1063/1.4944344Additional Authors: Marchenko, T.;Miron, C.;Patanen, M.;Osipov, T.;Schorb, S.;Simon, M.;Swiggers, M.;Techert, S.;Ueda, K.;Bostedt, C.;Rolles, D.;Rudenko, A.Ultrafast electron transfer in dissociating iodomethane and fluoromethane molecules was studied at the Linac Coherent Light Source free-electron laser using an ultraviolet-pump, X-ray-probe scheme. The results for both molecules are discussed with respect to the nature of their UV excitation and different chemical properties. Signatures of long-distance intramolecular charge transfer are observed for both species, and a quantitative analysis of its distance dependence in iodomethane is carried out for charge states up to I21+. The reconstructed critical distances for electron transfer are in good agreement with a classical over-the-barrier model and with an earlier experiment employing a near-infrared pump pulse. © 2016 Author(s)

Strong damping of phononic heat current by magnetic excitations in SrCu_2(BO_3)_2

Measurements of the thermal conductivity as a function of temperature and magnetic field in the 2D dimer spin system SrCu$_2$(BO$_3$)$_2$ are presented. In zero magnetic field the thermal conductivity along and perpendicular to the magnetic planes shows a pronounced double-peak structure as a function of temperature. The low-temperature maximum is drastically suppressed with increasing magnetic field. Our quantitative analysis reveals that the heat current is due to phonons and that the double-peak structure arises from pronounced resonant scattering of phonons by magnetic excitations.Comment: a bit more than 4 pages, 2 figures included; minor changes to improve the clarity of the presentatio

Imaging Molecular Structure through Femtosecond Photoelectron Diffraction on Aligned and Oriented Gas-Phase Molecules

This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray Free-Electron Laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C8H5F) and dissociating, laseraligned 1,4-dibromobenzene (C6H4Br2) molecules and discuss them in the larger context of photoelectron diffraction on gas-phase molecules. We also show how the strong nanosecond laser pulse used for adiabatically laser-aligning the molecules influences the measured electron and ion spectra and angular distributions, and discuss how this may affect the outcome of future time-resolved photoelectron diffraction experiments.Comment: 24 pages, 10 figures, Faraday Discussions 17

Jitter-correction for IR/UV-XUV pump-probe experiments at the FLASH free-electron laser

Citation: Savelyev, E., Boll, R., Bomme, C., Schirmel, N., Redlin, H., Erk, B., . . . Rolles, D. (2017). Jitter-correction for IR/UV-XUV pump-probe experiments at the FLASH free-electron laser. New Journal of Physics, 19, 13. doi:10.1088/1367-2630/aa652dIn pump-probe experiments employing a free-electron laser (FEL) in combination with a synchronized optical femtosecond laser, the arrival-time jitter between the FEL pulse and the optical laser pulse often severely limits the temporal resolution that can be achieved. Here, we present a pump-probe experiment on the UV-induced dissociation of 2,6-difluoroiodobenzene (C6H3F2I) molecules performed at the FLASH FEL that takes advantage of recent upgrades of the FLASH timing and synchronization system to obtain high-quality data that are not limited by the FEL arrival-time jitter. Wediscuss in detail the necessary data analysis steps and describe the origin of the timedependent effects in the yields and kinetic energies of the fragment ions that we observe in the experiment

Single-molecule techniques in biophysics : a review of the progress in methods and applications

Single-molecule biophysics has transformed our understanding of the fundamental molecular processes involved in living biological systems, but also of the fascinating physics of life. Far more exotic than a collection of exemplars of soft matter behaviour, active biological matter lives far from thermal equilibrium, and typically covers multiple length scales from the nanometre level of single molecules up several orders of magnitude to longer length scales in emergent structures of cells, tissues and organisms. Biological molecules are often characterized by an underlying instability, in that multiple metastable free energy states exist which are separated by energy levels of typically just a few multiples of the thermal energy scale of kBT, where kB is the Boltzmann constant and T the absolute temperature, implying complex, dynamic inter-conversion kinetics across this bumpy free energy landscape in the relatively hot, wet environment of real, living biological matter. The key utility of single-molecule biophysics lies in its ability to probe the underlying heterogeneity of free energy states across a population of molecules, which in general is too challenging for conventional ensemble level approaches which measure mean average properties. Parallel developments in both experimental and theoretical techniques have been key to the latest insights and are enabling the development of highly-multiplexed, correlative techniques to tackle previously intractable biological problems. Experimentally, technological developments in the sensitivity and speed of biomolecular detectors, the stability and efficiency of light sources, probes and microfluidics, have enabled and driven the study of heterogeneous behaviours both in vitro and in vivo that were previously undetectable by ensemble methods..