Experimental station Bernina at SwissFEL: condensed matter physics on femtosecond time scales investigated by X-ray diffraction and spectroscopic methods

The Bernina instrument at the SwissFEL Aramis hard X-ray free-electron laser is designed for studying ultrafast phenomena in condensed matter and material science. Ultrashort pulses from an optical laser system covering a large wavelength range can be used to generate specific non-equilibrium states, whose subsequent temporal evolution can be probed by selective X-ray scattering techniques in the range 2-12keV. For that purpose, the X-ray beamline is equipped with optical elements which tailor the X-ray beam size and energy, as well as with pulse-to-pulse diagnostics that monitor the X-ray pulse intensity, position, as well as its spectral and temporal properties. The experiments can be performed using multiple interchangeable endstations differing in specialization, diffractometer and X-ray analyser configuration and load capacity for specialized sample environment. After testing the instrument in a series of pilot experiments in 2018, regular user operation begins in 2019.

Influence of the protein environment on spectroscopy and ultrafast dynamics of retinal in bacteriorhodopsin

Selma Schenkl

The environment is important for the exact course of a chemical reaction. As an example of the strong influence of the environment on the reaction, this work studies the isomerization reaction of the chromophore retinal in the binding pocket of the protein bacteriorhodopsin. Three selected distance scales with reference to the chromophore are addressed: The distant protein surface at a length scale of 3-5 nm, the fuzzy environment of the binding pocket (1-2 nm) and the immediate neighborhood represented by the amino acid tryptophan Trp86 (5 Å). First, static absorption and fluorescence spectroscopies are applied to three dimensionally crystallized bacteriorhodopsin. An especially adapted set-up was developed for each task. The analysis of data is carried out in comparison with the measured spectra of the native protein membrane in solution. While the absorption spectrum shows a broadening on the high-energy side, the fluorescence spectrum deviates in the general shape of that measured in solution. The synoptic analysis of all spectra reveals the existence of three spectroscopically distinct species in the crystal: BR490 (absorption maximum at 490 nm) with a relative contribution of 28%, BR570 (native spectrum of solution, 68%), and BR610 ("blue membrane", 4%). BR490 appears particularly in the additional fluorescence band at 550 nm and is assigned to the dehydrated species of bacteriorhodopsin. The presence of that particular species indicates the suppression of rehydration in a partially dehydrated crystal and shows that the three dimensional arrangement hinders water diffusion. A simple model, close domains are assumed to form, eventually suppressing free water diffusion in a crystal. The lack of water on the protein surface modifies the protonation states of the amino acids in the binding pocket and therefore the optical properties of the retinal. The chromophore actually reacts on the alteration of its distant environment upon incorporation in the protein crystal. The second distance scale - the fuzzy environment - is addressed by a time-integrated fluorescence spectroscopy on native bacteriorhodopsin as function of the excitation wavelength (430 nm to 650 nm). The optimized experimental set-up guaranteed that the fluorescence of only the excited state I460 contributed. The measured spectra show maxima at 740 nm, and exhibit a Stokes shift of 5000 cm-1, independent of the excitation wavelength. The similarity of the fluorescence excitation spectrum with the spectrum of absorbed photons excludes energy-dependent loss channels. However, the spectra show a growing asymmetric broadening on the high-energy side with decreasing excitation wavelength. The additional fluorescence originates from vibrational hot states, also supported by the decomposition by Gaussian functions. A comparison with the fluorescence spectrum of blue membranes shows that the low-energy part also arises from vibrational hot states. Consequently, the first fast intramolecular vibrational energy relaxation does not entirely distribute the access-energy to other modes. The remaining energy is found in a quasi-static occupation of vibrational modes. The subsequent second vibrational relaxation — probably not only involving the retinal but also the protein — takes place on a time scale similar to that of the isomerization. The fast isomerization reaction prevents dissipation of energy relaxation of the excited state of the retinal into the protein environment. On a third distance scale, femtosecond spectroscopy in the UV offers a direct view into the electrostatic interaction of the chromophore with its immediate neighborhood. For the first time, the retinal isomerization was studied within the spectral window of the tryptophan absorption from 265 nm to 310 nm. For this, a set-up adapted to UV wavelengths was realized, basing on non-linear optics. The developed single-shot detection system yields a sensitivity of 10-5 in optical density. In the transient absorption measurements, a time resolution of 90 fs was achieved. At short probe wavelengths (265 nm - 294 nm), the measured transients show first a fast reduction of the absorption which subsequently recovers on three time scales (380 fs, 3 ps, > 16 ps). With increasing probe wavelength an induced transient absorption becomes dominant (282 nm - 294 nm). It has a rise time of 280 fs, and decays with a time constant of 4.3 ps. With further increasing probe wavelength the absorption signal decays faster. In response to the complex signature of the transients, an iterative and model-independent transient-decomposition is introduced. A set of three basis elements were identified: one bleach, and two absorption transients. The two induced absorption transients are assigned to retinal. The dynamics of the excited state (I460) in the first retinal-transient is described by two time constants (280 fs and 1 ps). The fast time constant leads to the photoproduct, while the slower one leads back to the ground state, presumably by internal conversion. The 250 fs delayed onset of the second transient (photo-intermediate J) is connected to a wave packet motion in the excited state. This delayed onset of the transient was observed for the first time. It demands a rise time of the J photo-intermediate of only 280 fs. This contrasts common estimates of 500 fs given in literature. For the first time, the temporal behavior of the permanent dipole moment of retinal is observed experimentally. Its evolution is imprinted in the dominant bleach feature (265 nm - 294 nm), originating from tryptophan Trp86. In the excited state, the permanent dipole moment increases strongly within the first 250 fs, and decays exponentially afterwards, following the formation of the photoproduct. However, the related time constant of 380 fs is slightly greater than that of 280 fs of the photoproduct J. This discrepancy may indicate a remaining long-lived polarization of the binding pocket. In brief, by using the intrinsic tryptophan as a probe, the local evolution of the electric field during the isomerization reaction was investigated. Indeed the isomerization reaction is reflected in the immediate environment. The variety of optical spectroscopy provides methods especially adapted for studying the influences of the environment on a chemical reaction. The results achieved here highlight the importance of these influences.

EPFL2004

Neutron spectroscopy in the layered quantum magnet SrCu₂(BO₃)₂ and in transition metal phosphorus trisulfides (MPS₃)

Diane Virginie Marie Lançon

Collective magnetic excitations are a fascinating aspect of condensed matter physics, where neutron scattering can provide valuable insight into the magnetic properties of physical realisations of model systems. This thesis focuses on the excitation spectra of layered quantum magnets in the case of the frustrated quantum magnet SrCu

_2

(BO

_3

)

_2

and the family of quasi-2D antiferromagnets MPS

_3

, with M a transition metal. \begin{itemize}[topsep=2pt,itemsep=-0.7ex] \item SrCu

_2

(BO

_3

)

_2

is a physical realisation of the two-dimensional Shastry-Sutherland theoretical model, constructed as orthogonal dimers with the product of singlets on the strong antiferromagnetic

J

bond as an exact ground state. The spin interactions for such a particular geometry induces strong frustration which leads to unconventional magnetism and exotic phases of matter. This work is concerned with a series of aspects of the magnetic excitations in this compound. The excitation spectra as a function of field, temperature and pressure are measured using neutron time-of-flight spectroscopy. The experimental results show that correlations, bound magnons and finite temperature properties are highly unconventional and these results are compared with existing theories on frustrated model systems. In addition, predicted topological properties of SrCu

_2

(BO

_3

)

_2

in an applied field are confirmed experimentally. \item The transition metal phosphorus trisulfides (MPS

_3

) are a family of quasi two-dimensional materials on a honeycomb lattice with weakly bound magnetic planes. This work focuses mainly on the exchange interactions and critical properties of FePS

_3

, which is largely anisotropic with the S=2 Fe

^{2+}

moments pointing normal to the

(a,b)

plane. Inelastic neutron scattering on single crystals is used to measure the spin wave dispersion, providing new insight on the strength of the coupling interactions and anisotropies and showing that FePS

_3

is a good two-dimensional model antiferromagnet. Similar experiments on powdered samples of NiPS

_3

show low-Q dispersive spin waves with a small spin-gap. Critical properties of FePS

_3

close to the Néel temperature are further discussed, as the magnetic nature of the measured quasi-elastic scattering is confirmed. Based on magnetization measurements in high pulsed fields, a possible tricritical point in the 40-50T range is proposed. \end{itemize} The work presented in this thesis has been carried out in a collaboration between the Institut Laue Langevin in Grenoble and the Laboratory for Quantum Magnetism of the EPFL.

EPFL2017

Spectroscopic Studies of the Electronic Structure in Layered Cuprates and Ruthenates

Claudia Giuseppina Fatuzzo

In materials where electrons interact strongly, a number of exotic and exciting phenomena arise. The mechanisms at the base of many of these phenomena remain debated, as strongly correlated electron physics represents one of the biggest challenges for modern condensed matter physics. Transition metal oxides are a class of strongly correlated systems which exhibit a multitude of physical properties, among which unconventional superconductivity, incommensurate charge and spin ordering, partial anisotropic gapping, strangemetallicity, colossal magnetoresistance, multiferroicity, antiferromagneticMott insulation, etc.. These properties are often observed in close vicinity, when pressure, temperature or chemical composition are varied. As a consequence, it is challenging to disentangle not only their origin, but also their effects on the elementary excitations of the system. In this thesis, high quality single crystals of copper and ruthenium based transition metal oxides (cuprate and ruthenate compounds) were investigated with synchrotron-based spectroscopic techniques. Our angle resolved photoemission spectroscopy (ARPES) studies focused on the normal state of cuprates, at hole content varying from under- to over-doping. First, the low energy single particle excitations in overdoped uprates were verified to fulfill the mathematical conditions for Landau Fermi quasiparticles. In a second study, the evolution of the spectral gap was followed as function of doping and temperature, across the charge order, pseudogap and strangcuprates, ruthenates, strong correlations, RIXS, ARPES, XAS, pseudogap, strange metal, spin orbit coupling, crystal field.e metal phases of a cuprate compound, La1.6¡xNd0.4SrxCuO4. This systematic study allowed the identification of an optimal doping regime for the investigation of the pseudogap physics in cuprates. The orbital structure of single layer ruthenates was explored combining X-ray absorption and resonant inelastic X-ray spectroscopies (XAS and RIXS). Since spectroscopies at the L absorption edge of 4d materials are challenged by insufficient energy resolution, we performed our studies at the oxygen K edge, in the soft X-ray energy range. By exploiting the strong orbital hybridization between the oxygen 2p and the ruthenium 4d states, we obtained high resolution experimental access to the 4d electron properties. The results were interpreted through a simple model Hamiltonian, with analytic solutions that provide a consistent description of the low energy features observed.

EPFL2017

Neutron spectroscopy in the layered quantum magnet SrCu₂(BO₃)₂ and in transition metal phosphorus trisulfides (MPS₃)

Diane Virginie Marie Lançon

_2

(BO

_3

)

_2

and the family of quasi-2D antiferromagnets MPS

_3

, with M a transition metal. \begin{itemize}[topsep=2pt,itemsep=-0.7ex] \item SrCu

_2

(BO

_3

)

_2

is a physical realisation of the two-dimensional Shastry-Sutherland theoretical model, constructed as orthogonal dimers with the product of singlets on the strong antiferromagnetic

J

_2

(BO

_3

)

_2

in an applied field are confirmed experimentally. \item The transition metal phosphorus trisulfides (MPS

_3

) are a family of quasi two-dimensional materials on a honeycomb lattice with weakly bound magnetic planes. This work focuses mainly on the exchange interactions and critical properties of FePS

_3

, which is largely anisotropic with the S=2 Fe

^{2+}

moments pointing normal to the

(a,b)

_3

is a good two-dimensional model antiferromagnet. Similar experiments on powdered samples of NiPS

_3

show low-Q dispersive spin waves with a small spin-gap. Critical properties of FePS

_3

EPFL2017

Spectroscopic Studies of the Electronic Structure in Layered Cuprates and Ruthenates

Claudia Giuseppina Fatuzzo

EPFL2017

Influence of the protein environment on spectroscopy and ultrafast dynamics of retinal in bacteriorhodopsin

Selma Schenkl

EPFL2004