arXiv subjects

Markus E. Gruner

Publications and source records attributed to Markus E. Gruner.

At least 19 recordsLinked to original sources

arXiv2026

Disentangling the dynamics of transient spin and orbital magnetization in SrTiO$_3$ via the inverse Faraday effect from RT-TDDFT

Motivated by recent evidence of ferroelectricity and even multiferroicity in the prototypical diamagnetic band insulator SrTiO$_3$ from terahertz experiments, we investigate the carrier and magnetization dynamics of SrTiO$_3$ excited optically by linearly (LPL) and circularly polarized light (CPL). Our RT-TDDFT simulations show a pronounced site- and orbital-dependent charge transfer from O$2p$ to Ti $3d$ states. With LPL anti-phase oscillations of the electron-density lobes at O and Ti resemble the soft transverse optical phonon mode and break dynamically inversion symmetry. CPL instead drives a coherent rotation of the charge dipoles around oxygen, producing a helicity-dependent transient magnetization of opposite sign at O and Ti, even without ionic motion. The dominant effect stems from the transfer of angular momentum (AM) from light to the electronic orbital AM, while spin-orbit coupling plays a key role in the transfer from orbital to spin AM, the former being an order of magnitude larger than the latter. The real-time resolution allows us to disentangle the inverse Faraday effect, which follows the pulse envelope, from optical orientation, which builds up during the pulse and saturates afterwards. The results demonstrate that purely electronic processes without lattice motion induce ultrafast magnetisation in a non magnetic insulator, offering a tunable route for light controlled magnetic functionalities.

cond-mat.mtrl-sci↗

arXiv2025

Sub-nanosecond structural dynamics of the martensitic transformation in Ni-Mn-Ga

Martensitic transformations drive a multitude of emerging applications, which range from high stroke actuation and, mechanocaloric refrigeration, to thermoelastic energy harvesting. All these applications benefit from faster transformations, as a high cycle frequency is essential for achieving high power density. However, systematic investigations of the fast dynamics and fundamental speed limits of martensitic transformations are scarce. Especially for ultrashort time transformations, the temperature evolution throughout the transformation is not measured, which is a substantial shortcoming as temperature is the intrinsic force driving the transformation. Here, we present a synchrotron-based time-resolved X-ray diffraction study of a 270 fs laser-induced martensitic transformation in a Ni-Mn-Ga-based epitaxial thin film. We observe the transformation from martensite to austenite within about 100 ps, just limited by the synchrotron probe pulse duration. Furthermore, a full transformation cycle from martensite to austenite and back to martensite can almost be finished within 5 ns, which is the fastest martensitic transformation reported so far. Measurements and calculations of the temperature evolution allow us to analyse the influence of temperature on transformation time. By time-resolved strain measurements we demonstrate that in addition to temperature, thermal film stress must be considered as a competing influence on the martensitic transformation. Our experimental findings are supported by molecular dynamics simulations with machine learned force fields adapted to density functional theory calculations. These reveal that the huge distortion during a martensitic transformation requires the collective movement of many atoms within the microstructure, which delays the transformation.

cond-mat.mtrl-sci↗

arXiv2023

Spatio-Temporal Electron Propagation Dynamics in Au/Fe/MgO(001) in nonequilibrium: Revealing Single Scattering Events and the Ballistic Limit

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.

cond-mat.mtrl-sci↗

arXiv2023

Local magnetic and geometric structure in Mn-doped La(Fe,Si)13

Magnetic cooling has the potential to replace conventional gas compression refrigeration. Materials such as La(Fe,Si)$_{13}$ exhibit a sizeable first-order magnetocaloric effect, and it is possible to tailor the phase transition towards room temperature by Mn-H-doping, resulting in a large temperature range for operation. Within this work, we discuss variations of the electronic and lattice structure in La(Fe,Si)$_{13}$ with increasing Mn content utilizing X-ray magnetic circular dichroism (XMCD) and extended X-ray absorption fine structure spectroscopy (EXAFS). While XMCD shows a decrease of the magnetic polarization at the Fe K edge, low-temperature EXAFS measurements indicate increased positional disorder in the La environment that is otherwise absent for Fe and Mn. First-principles calculations link the positional disorder to an enlarged Mn-Si distance -- explaining the increased positional disorder in the La surrounding.

cond-mat.mtrl-sci↗

arXiv2023

Dissipation losses limiting first-order phase transition materials in cryogenic caloric cooling: A case study on all-d-metal Ni(-Co)-Mn-Ti Heusler alloys

Ni-Mn-based Heusler alloys, in particular all-d-metal Ni(-Co)-Mn-Ti, are highly promising materials for energy-efficient solid-state refrigeration as large multicaloric effects can be achieved across their magnetostructural martensitic transformation. However, no comprehensive study on the crucially important transition entropy change $Δs_t$ exists so far for Ni(-Co)-Mn-Ti. Here, we present a systematic study analyzing the composition and temperature dependence of $Δs_t$. Our results reveal a substantial structural entropy change contribution of approximately 65 J(kgK)$^{-1}$, which is compensated at lower temperatures by an increasingly negative entropy change associated with the magnetic subsystem. This leads to compensation temperatures $T_{comp}$ of 75 K and 300 K in Ni$_{35}$Co$_{15}$Mn$_{50-y}$Ti$_{y}$ and Ni$_{33}$Co$_{17}$Mn$_{50-y}$Ti$_{y}$, respectively, below which the martensitic transformations are arrested. In addition, we simultaneously measured the responses of the magnetic, structural and electronic subsystems to the temperature- and field-induced martensitic transformation near $T_{comp}$, showing an abnormal increase of hysteresis and consequently dissipation energy at cryogenic temperatures. Simultaneous measurements of magnetization and adiabatic temperature change $ΔT_{ad}$ in pulsed magnetic fields reveal a change in sign of $ΔT_{ad}$ and a substantial positive and irreversible $ΔT_{ad}$ up to 15 K at 15 K as a consequence of increased dissipation losses and decreased heat capacity. Most importantly, this phenomenon is universal, it applies to any first-order material with non-negligible hysteresis and any stimulus, effectively limiting the utilization of their caloric effects for gas liquefaction at cryogenic temperatures.

cond-mat.mtrl-sci↗

arXiv2022

Anisotropic carrier dynamics in a laser-excited Fe$_{1}$/(MgO)$_{3}$(001) heterostructure from real-time time-dependent DFT

The interaction of a femtosecond optical pulse with a Fe$_{1}$/(MgO)$_{3}$(001) metal/oxide heterostructure is investigated using time-dependent density functional theory (TDDFT) calculations in the real-time domain. We systematically study electronic excitations as a function of laser frequency, peak power density and polarization direction. While spin-orbit coupling is found to result in only a small time-dependent reduction of magnetization (less than 10%), we find a marked anisotropy in the response to in-plane and out-of-plane polarized light, which changes its character qualitatively depending on the excitation energy: the Fe-layer is efficiently addressed at low frequencies by in-plane polarized light, whereas for frequencies higher than the MgO band gap, we find a particularly strong response of the central MgO-layer for cross-plane polarized light. For laser excitations between the charge transfer gap and the MgO band gap, the interface plays the most important role, as it mediates concerted transitions from the valence band of MgO into the $3d$ states of Fe closely above the Fermi level and from the Fe-states below the Fermi level into the conduction band of MgO. As these transitions can occur simultaneously altering charge balance of the layers, they could potentially lead to an efficient transfer of excited carriers into the MgO bulk, where the corresponding electron and hole states can be separated by an energy which is significantly larger than the photon energy.

cond-mat.mtrl-sci↗

arXiv2021

Impact of local arrangement of Fe and Ni on the phase stability and magnetocrystalline anisotropy in Fe-Ni-Al Heusler alloys

On the basis of density functional calculations, we report on a comprehensive study of the influences of atomic arrangement and Ni substitution for Al on the ground state structural and magnetic properties for Fe$_2$Ni$_{1+x}$Al$_{1-x}$ Heusler alloys. We discuss systematically the competition between five Heusler-type structures formed by shuffles of Fe and Ni atoms and their thermodynamic stability. All~Ni-rich Fe$_2$Ni$_{1+x}$Al$_{1-x}$ tend to decompose into a dual-phase mixture consisting of Fe$_2$NiAl and~FeNi. The~successive replacement of Ni by Al leads to a change of ground state structure and eventually an increase in magnetocrystalline anisotropy energy~(MAE). We predict for stoichiometric Fe$_2$NiAl a ground state structure with nearly cubic lattice parameters but alternating layers of Fe and Ni possessing an uniaxial MAE which is even larger than tetragonal L1$_0$-FeNi. This opens an alternative route for improving the phase stability and magnetic properties in FeNi-based permanent magnets.

cond-mat.mtrl-sci↗

arXiv2021

Impact of local arrangement of Fe and Ni in Fe-Ni-Al Heusler alloys on the phase stability and magnetocrystalline anisotropy

On the basis of the density functional calculations in combination with the supercell approach, we report on a complete study of the influences of atomic arrangement and Ni substitution for Al on the ground state structural and magnetic properties for Fe$_2$Ni$_{1+x}$Al$_{1-x}$ Heusler alloys. We discuss systematically the competition between five cubic Heusler-type structures formed by shuffles of Fe and Ni atoms to reveal routes for improving the phase stability and magnetic properties, in particular magnetocrystalline anisotropy~(MAE). We predict that in case of Fe$_2$NiAl the ground state cubic structure with alternated layers of Fe and Ni possesses the highest uniaxial MAE which twice larger than that for the tetragonal L1$_0$ FeNi. The successive Ni doping at Al sublattice leads to a change of ground state structure and to reduce of the MAE. In addition, the phase stability against the decomposition into the stable systems at finite-temperatures is discussed. All~Ni-rich Fe$_2$Ni$_{1+x}$Al$_{1-x}$ are turned to be decomposed into a dual-phase consisting of Fe$_2$NiAl and FeNi.

cond-mat.mtrl-sci↗

arXiv2021

Theoretical description of optical and X-ray absorption spectra of MgO including many-body effects

Here we report the optical and x-ray absorption (XAS) spectra of the wide-band-gap oxide MgO using density functional theory (DFT) and many-body perturbation theory (MBPT). Our comprehensive study of the electronic structure shows that while the band gap is underestimated with the exchange-correlation functional PBEsol (4.58 eV) and the hybrid functional HSE06 (6.58 eV) compared to the experimental value (7.7 eV), it is significantly improved (7.52 eV) and even overcompensated (8.53 eV) when quasiparticle corrections are considered. Inclusion of excitonic effects by solving the Bethe-Salpeter equation (BSE) yields the optical spectrum in excellent agreement with experiment. Excellent agreement is observed also for the O and Mg K-edge absorption spectra, demonstrating the importance of the electron-hole interaction within MBPT. Projection of the electron-hole coupling coefficients from the BSE eigenvectors on the band structure allows us to determine the origin of prominent peaks and identify the orbital character of the relevant contributions. The real space projection of the lowest energy exciton wavefunction of the optical spectrum indicates a Wannier-Mott type, whereas the first exciton in the O K-edge is more localized.

cond-mat.other↗

arXiv2020

Interface-related magnetic and vibrational properties in Fe/MgO heterostructures from nuclear resonant spectroscopy and first-principles calculations

We combine $^{57}$Fe Mössbauer spectroscopy and $^{57}$Fe nuclear resonant inelastic x-ray scattering (NRIXS) in nanoscale polycrystalline [bcc-$^{57}$Fe/MgO] multilayers with various Fe layer thicknesses and layer-resolved density-functional-theory (DFT) based first-principles calculations of a (001)-oriented [Fe(8 ML)/MgO(8 ML)](001) heterostructure to unravel the interface-related atomic vibrational properties of a multilayer system. In theory and experiment, we observe consistently enhanced hyperfine magnetic fields compared to bulk which are associated with the Fe/MgO interface layers. NRIXS and DFT both reveal a strong reduction of the longitudinal acoustic (LA) phonon peak in combination with an enhancement of the low-energy vibrational density of states (VDOS) suggesting that the presence of interfaces and the associated increase in the layer-resolved magnetic moments results in drastic changes in the Fe-partial VDOS. From the experimental and calculated VDOS, vibrational thermodynamic properties have been determined as a function of Fe thickness and are found to be in excellent agreement.

cond-mat.mtrl-sci↗

arXiv2019

Influence of hydrogenation on the vibrational density of states of magnetocaloric $\mathrm{LaFe}_\mathrm{11.4}\mathrm{Si}_\mathrm{1.6}\mathrm{H}_{1.6}$

We report on the impact of magnetoelastic coupling on the magnetocaloric properties of LaFe$_{11.4}$Si$_{1.6}$H$_{1.6}$ in terms of the vibrational density of states, which we determined with $^{57}$Fe nuclear resonant inelastic X-ray scattering measurements and with density-functional-theory based first-principles calculations in the ferromagnetic low-temperature and paramagnetic high-temperature phase. In experiments and calculations, we observe pronounced differences in the shape of the Fe-partial VDOS between non-hydrogenated and hydrogenated samples. This shows that hydrogen does not only shift the temperature of the first-order phase transition, but also affects the elastic response of the Fe-subsystem significantly. In turn, the anomalous redshift of the Fe VDOS, observed by going to the low-volume PM phase, survives hydrogenation. As a consequence, the change in the Fe specific vibrational entropy $ΔS_\mathrm{lat}$ across the phase transition has the same sign as the magnetic and electronic contribution. DFT calculations show that the same mechanism, which is a consequence of the itinerant electron metamagnetism associated with the Fe subsystem, is effective in both the hydrogenated and he hydrogen-free compounds. Although reduced by 50 % as compared to the hydrogen-free system, the measured change $ΔS_\mathrm{lat}$ of 3.2\pm1.9 J/kgK across the FM to PM transition contributes with 35 % significantly and cooperatively to the total isothermal entropy change $ΔS_\mathrm{iso}$. Hydrogenation is observed to induce an overall blueshift of the Fe-VDOS with respect to the H-free compound; this effect, together with the enhanced Debye temperature observed, is a fingerprint of the hardening of the Fe sublattice by hydrogen incorporation. In addition, the mean Debye velocity of sound of LaFe$_{11.4}$Si$_{1.6}$H$_{1.6}$ was determined from the NRIXS and the DFT data.

cond-mat.mtrl-sci↗

arXiv2019

Epitaxial strain adaption in chemically disordered FeRh thin films

Strain and strain adaption mechanisms in modern functional materials are of crucial importance for their performance. Understanding these mechanisms will advance innovative approaches for material properties engineering. Here we study the strain adaption mechanism in a thin film model system as function of epitaxial strain. Chemically disordered FeRh thin films are deposited on W-V buffer layers, which allow for large variation of the preset lattice constants, e.g. epitaxial boundary condition. It is shown by means of high resolution X-ray reciprocal space maps and transmission electron microscopy that the system reacts with a tilting mechanism of the structural units in order to adapt to the lattice constants of the buffer layer. This response explained by density functional theory calculations, which evidence an energetic minimum for structures with a distortion of c/a =0.87. The experimentally observed tilting mechanism is induced by this energy gain and allows the system to remain in the most favorable structure. In general, it is shown that the use of epitaxial model heterostructures consisting of alloy buffer layers of fully miscible elements and the functional material of interest allows to study strain adaption behaviors in great detail. This approach makes even small secondary effects observable, such as the directional tilting of the structural domains identified in the present case study.

cond-mat.mtrl-sci↗

arXiv2017

Interplay of phase sequence and electronic structure in the modulated martensites of Mn$_2$NiGa from first-principles

We investigate relative stability, structural properties and electronic structure of various modulated martensites of the magnetic shape memory alloy Mn$_{2}$NiGa by means of density functional theory. We observe that the instability in the high-temperature cubic structure first drives the system to a structure where modulation shuffles with a period of six atomic planes are taken into account. The driving mechanism for this instability is found to be the nesting of the minority band Fermi surface, in a similar way as established for the prototype system Ni$_{2}$MnGa. In agreement with experiments, we find 14M modulated structures with orthorhombic and monoclinic symmetries having energies lower than other modulated phases with same symmetry. In addition, we also find energetically favourable 10M modulated structures which have not been observed experimentally for this system yet. The relative stability of various martensites is explained in terms of changes in the electronic structures near the Fermi level, affected mostly by the hybridisation of Ni and Mn states. Our results indicate that the maximum achievable magnetic field-induced strain in Mn$_{2}$NiGa would be larger than in Ni$_{2}$MnGa. However, the energy costs for creating nanoscale adaptive twin boundaries are found to be one order of magnitude higher than that in Ni$_{2}$MnGa.

cond-mat.mtrl-sci↗

arXiv2017

Ordering tendencies and electronic properties in quaternary Heusler derivatives

The phase stabilities and ordering tendencies in the quaternary full-Heusler alloys NiCoMnAl and NiCoMnGa have been investigated by in-situ neutron diffraction, calorimetry and magnetization measurements. NiCoMnGa was found to adopt the L2$_1$ structure, with distinct Mn and Ga sublattices but a common Ni-Co sublattice. A second-order phase transition to the B2 phase with disorder also between Mn and Ga was observed at 1160 K. In contrast, in NiCoMnAl slow cooling or low-temperature annealing treatments are required to induce incipient L2$_1$ ordering, otherwise the system displays only B2 order. Linked to this L2$_1$ ordering, a drastic increase in the magnetic transition temperature was observed in NiCoMnAl, while annealing affected the magnetic behavior of NiCoMnGa only weakly due to the low degree of quenched-in disorder. First principles calculations were employed to study the thermodynamics as well as order-dependent electronic properties of both compounds. It was found that a near half-metallic pseudo-gap emerges in the minority spin channel only for the completely ordered Y structure, which however is energetically unstable compared to the predicted ground state of a tetragonal structure with alternating layers of Ni and Co. The experimental inaccessibility of the totally ordered structures is explained by kinetic limitations due to the low ordering energies.

cond-mat.str-el↗

arXiv2017

Modulations in martensitic Heusler alloys originate from nanotwin ordering

Heusler alloys exhibiting magnetic and martensitic transitions enable applications like magnetocaloric refrigeration and actuation based on the magnetic shape memory effect. Their outstanding functional properties depend on low hysteresis losses and low actuation fields. These are only achieved if the atomic positions deviate from a tetragonal lattice by periodic displacements. The origin of the so-called modulated structures is the subject of much controversy: They are either explained by phonon softening or adaptive nanotwinning. Here we used large-scale density functional theory calculations on the Ni2MnGa prototype system to demonstrate interaction energy between twin boundaries. Minimizing the interaction energy resulted in the experimentally observed ordered modulations at the atomic scale, it explained that a/b twin boundaries are stacking faults at the mesoscale, and contributed substantially to the macroscopic hysteresis losses. Furthermore, we found that phonon softening paves the transformation path towards the nanotwinned martensite state. This unified both opposing concepts to explain modulated martensite.

cond-mat.mtrl-sci↗

arXiv2016

Impact of lattice dynamics on the phase stability of metamagnetic FeRh: Bulk and thin films

We present phonon dispersions, element-resolved vibrational density of states (VDOS) and corresponding thermodynamic properties obtained by a combination of density functional theory (DFT) and nuclear resonant inelastic X-ray scattering (NRIXS) across the metamagnetic transition of B2 FeRh in the bulk material and thin epitaxial films. We see distinct differences in the VDOS of the antiferromagnetic (AF) and ferromagnetic (FM) phase which provide a microscopic proof of strong spin-phonon coupling in FeRh. The FM VDOS exhibits a particular sensitivity to the slight tetragonal distortions present in epitaxial films, which is not encountered in the AF phase. This results in a notable change in lattice entropy, which is important for the comparison between thin film and bulk results. Our calculations confirm the recently reported lattice instability in the AF phase. The imaginary frequencies at the $X$-point depend critically on the Fe magnetic moment and atomic volume. Analyzing these non vibrational modes leads to the discovery of a stable monoclinic ground state structure which is robustly predicted from DFT but not verified in our thin film experiments. Specific heat, entropy and free energy calculated within the quasiharmonic approximation suggest that the new phase is possibly suppressed because of its relatively smaller lattice entropy. In the bulk phase, lattice degrees of freedom contribute with the same sign and in similar magnitude to the isostructural AF-FM phase transition as the electronic and magnetic subsystems and therefore needs to be included in thermodynamic modeling.

cond-mat.mtrl-sci↗

arXiv2016

Tailoring Magnetic Frustration in Strained Epitaxial FeRh Films

We report on a strain-induced martensitic transformation, accompanied by a suppression of magnetic order in epitaxial films of chemically disordered FeRh. X-ray diffraction, transmission electron microscopy and electronic structure calculations reveal that the lowering of symmetry (from cubic to tetragonal) imposed by the epitaxial relation leads to a further, unexpected, tetragonal-to-orthorhombic transition, triggered by a band-Jahn-Teller-type lattice instability. The collapse of magnetic order is a direct consequence of this structural change, which upsets the subtle balance between ferromagnetic nearest-neighbor interactions arising from Fe-Rh hybridization and frustrated antiferromagnetic coupling among localized Fe moments at larger distances.

cond-mat.mtrl-sci↗

arXiv2014

First-principles calculation of the instability leading to giant inverse magnetocaloric efects

The structural and magnetic properties of functional Ni-Mn-Z (Z = Ga, In, Sn) Heusler alloys are studied by first-principles and Monte Carlo methods. The \textit{ab initio} calculations give a basic understanding of the underlying physics which is associated with the strong competition of ferro- and antiferromagnetic interactions with increasing chemical disorder. The resulting $d$-electron orbital dependent magnetic ordering is the driving mechanism of magnetostructural instability which is accompanied by a drop of magnetization governing the size of the magnetocaloric effect. The thermodynamic properties are calculated by using the \textit{ab initio} magnetic exchange coupling constants in finite-temperature Monte Carlo simulations, which are used to accurately reproduce the experimental entropy and adiabatic temperature changes across the magnetostructural transition.

cond-mat.mtrl-sci↗