Searching for Laves Phase Superstructures: Structural and 27Al NMR Spectroscopic Investigations in the Hf-V-Al System.

Laves phases exhibit a plethora of different structures and a multitude of physical properties. Investigations in the ternary system Hf-V-Al led to the discovery of numerous members of the solid solution Hf(V1-xAlx)2, which adopt the hexagonal MgZn2 type (C14) for medium to high amounts of Al (x = 0.2-1) and the cubic MgCu2 type (C15) for small Al amounts (x = 0.05-0.1). While all members exhibit Pauli-paramagnetic behavior due to the absence of localized magnetic moments, the V-rich cubic member Hf(V0.95Al0.05)2 additionally exhibits a superconducting state below TC = 7.6(1) K. All synthesized compounds were characterized by powder X-ray diffraction, and selected samples were furthermore investigated by 27Al solid-state magic-angle spinning (MAS) NMR. HfAl2 exhibits two Al resonances, one rather sharp and one significantly broadened signal, in line with the crystal structure and respective coordination environments. The members of the solid solution exhibit extremely broadened resonances due to the mixing of V and Al on the same crystallographic sites. For nominal Hf(V0.125Al0.875)2, however, two distinct sharp NMR signals were observed. This contrasts with the description of a solid solution. Therefore, single-crystal X-ray studies were conducted, showing that Hf(V0.125Al0.875)2 really is an ordered compound with the sum formula Hf4VAl7 (P3̅m1), which exhibits an, thus far, unknown superstructure of MgZn2.

Formation of the Sub-oxide Sc4Au2O1-x and the Drastically Negative 27Al NMR Shift in Sc2Al.

During attempts to synthesize Sc4AuAl in the cubic Gd4RhIn-type structure, the solid solution Sc2Au0.5Al0.5 in the PbCl2-type structure formed instead. Subsequently, the solid solution Sc2Au1-xAlx was investigated with respect to its existence range along with the structure types formed for different compositions with x = 0, 0.25, 0.5, 0.75, and 1. According to X-ray powder diffraction studies, Sc2Al and nominal Sc2Au0.25Al0.75 crystallized in the hexagonal Ni2In-type structure (P63/mmc), while Sc2Au0.5Al0.5, Sc2Au0.75Al0.25, and Sc2Au were found to crystallize in the orthorhombic PbCl2-type structure (Pnma). The crystal structures of Sc2Au and Sc2Au0.59(1)Al0.41(1) were refined from single-crystal data (Sc2Au: a = 648.0(1), b = 467.2(1), c = 835.2(2) pm, wR2 = 0.0382, 535 F2 values, 25 variables; Sc2Au0.59(1)Al0.41(1): a = 632.48(5), b = 472.16(3), c = 848.67(6) pm, wR2 = 0.0484, 540 F2 values, 21 variables). Contamination with air during the synthesis of Sc2Au led to the discovery of a compound adopting the cubic W4Co2C-type structure (stuffed cubic Ti2Ni type). Using Sc2O3 as a defined oxygen source led to samples with high amounts of Sc4Au2O1-x. All intermetallic compounds exhibited Pauli paramagnetic behavior in the investigated temperature range of 2.1 to 300 K, and no superconductivity was observed at low temperatures and low fields. Sc2Au and Sc2Al were investigated by 27Al and 45Sc solid-state NMR investigations. For Sc2Al, one signal was found in the 27Al NMR spectra in line with the crystal structure; however, an extremely negative resonance shift of δ = -673 ppm was observed. In both compounds, two Sc resonances were observed, in line with the proposed crystal structure. Finally, it was observed that the stability of Sc2Au in air is limited. This was investigated via thermal analysis and (temperature-dependent) powder X-ray diffraction. DFT calculations helped in assessing charge analysis, electronic properties, and chemical bonding.

Prediction of Novel Ultrahard Phases in the B-C-N System from First Principles: Progress and Problems.

The modern synthesis of superhard and, especially, ultrahard phases is a fascinating area of research that could lead to the design of new, industrially important materials. Computational methods built within the well-established quantum mechanics framework of density functional theory (DFT) play an important role in the search for these advanced materials and the prediction of their properties. The close relationship between the physical properties of carbon and boron nitride has led to particular interest in the B-C-N ternary system, characterized by the small radii of the elements, resulting in short interatomic distances and reduced volumes-the parameters being 'recipes' for very high hardness in three-dimensional structures. The purpose of this review is to provide a brief outline of recent developments and problems in predicting novel ultrahard carbon allotropes as well as binary and ternary compounds of the B-C-N system with particular emphasis on the analysis of the models used to evaluate the hardness of the theoretically predicted structures.

Charge transfer driven by ultrafast spin transition in a CoFe Prussian blue analogue.

Photoinduced charge-transfer is an important process in nature and technology and is responsible for the emergence of exotic functionalities, such as magnetic order for cyanide-bridged bimetallic coordination networks. Despite its broad interest and intensive developments in chemistry and material sciences, the atomic-scale description of the initial photoinduced process, which couples intermetallic charge-transfer and spin transition, has been debated for decades; it has been beyond reach due to its extreme speed. Here we study this process in a prototype cyanide-bridged CoFe system by femtosecond X-ray and optical absorption spectroscopies, enabling the disentanglement of ultrafast electronic and structural dynamics. Our results demonstrate that it is the spin transition that occurs first on the Co site within ~50 fs, and it is this that drives the subsequent Fe-to-Co charge-transfer within ~200 fs. This study represents a step towards understanding and controlling charge-transfer-based functions using light.

Direct observation of nuclear reorganization driven by ultrafast spin transitions.

One of the most basic molecular photophysical processes is that of spin transitions and intersystem crossing between excited states surfaces. The change in spin states affects the spatial distribution of electron density through the spin orbit coupling interaction. The subsequent nuclear reorganization reports on the full extent of the spin induced change in electron distribution, which can be treated similarly to intramolecular charge transfer with effective reaction coordinates depicting the spin transition. Here, single-crystal [FeII(bpy)3](PF6)2, a prototypical system for spin crossover (SCO) dynamics, is studied using ultrafast electron diffraction in the single-photon excitation regime. The photoinduced SCO dynamics are resolved, revealing two distinct processes with a (450 ± 20)-fs fast component and a (2.4 ± 0.4)-ps slow component. Using principal component analysis, we uncover the key structural modes, ultrafast Fe-N bond elongations coupled with ligand motions, that define the effective reaction coordinate to fully capture the relevant molecular reorganization.

Electronic and Magnetic Structures of New Interstitial Boron Sub-Oxides B12O2:X (X = B, C, N, O).

The boron-rich boron sub-oxide rhombohedral B6O considered in B12O2 full formulation has a large O-O spacing of ~3 Å and a central vacant position that can receive interstitial atoms X, forming a central O-X-O alignment in the dodecaboron cage as observed in well-known triatomic B12 compounds as B12{C-C-C}, B12{N-B-N}, etc. Plane wave density functional theory (DFT) based calculations of unrestricted geometry relaxation of B12{O-X-O}, X = B, C, N, and O let one identify new ternary sub-oxides, all found cohesive while showing different d(X-O) distances ranging from d(B-O) = 1.95 Å down to d(O-O) = 1.73 Å with intermediate d(C-O) = 1.88 Å. The different magnitudes were assigned to the chemical affinities of X-inserts versus host oxygen with the increasing development of X-O bonding along the series with larger cohesive B12{O-O-O}. From the atom projected charge density, B presents none, while significant magnitudes are shown on C and N, the latter developing bonding with terminal oxygen atoms especially N. The presence of unpaired valence electrons leaves nonbonding charge density on X = C, N interstitial compounds, which, besides the relative isolation of the central C and N lead to the onset of magnetic moments: M(C) = 1.9 µB, and M(N) = 1 µB in a ferromagnetic ground state. Atom-resolved assessments are provided with the magnetic charge density and electron localization function electron localization function (ELF) projections on one hand and the site and spin projected density of states and the chemical bonding based on the overlap integral Sij within the COOP criterion, on the other hand.

Correlations of Crystal and Electronic Structure via NMR and X-ray Photoelectron Spectroscopies in the RETMAl2 (RE = Sc, Y, La-Nd, Sm, Gd-Tm, Lu; TM = Ni, Pd, Pt) Series.

A total of 35 intermetallic aluminum compounds have been synthesized from the elements via arc melting and characterized by powder X-ray diffraction. A total of 15 of them have been previously reported; however, detailed property investigations were missing. Compounds of the RETMAl2 (rare earth metal RE = Sc, Y, La-Nd, Sm, Gd-Tm, Lu) series with transition metal TM = Ni, Pd, and Pt crystallize isostructurally in the orthorhombic MgCuAl2 type structure ( Cmcm, oC16, fc2). Single-crystal X-ray diffraction investigations were conducted on YNiAl2, LaNiAl2, YPdAl2, ScPtAl2, and YPtAl2. The TM and Al atoms form a [TMAl2]δ- polyanion, the RE atoms reside in cavities within the framework. While the Sc, Y, La, and Lu compounds exhibit Pauli-paramagnetic behavior, consistent with all atoms being closed shell, the other RETMAl2 compounds show paramagnetism along with magnetic ordering at low temperatures, in line with an open-shell trivalent oxidation state for the RE atoms. Solid-state 27Al NMR investigations were carried out on the Pauli-paramagnetic samples, all showing only a single central transition, in line with one crystallographic site for the respective atoms. The observed quadrupolar coupling constants and electric-field-gradient asymmetry parameters were found to be in good agreement with the density-functional-theory-calculated values. Isotropic resonance shifts are dominated by the Fermi-contact interactions with s-conduction electron densities at the Fermi edge (Knight shifts). The bonding characteristics mirror the electronic density of states and crystal chemistry of the family of intermetallic compounds under consideration. Both the Knight shifts and quadrupolar coupling constants can be predicted based on element-specific increments.

Electronic and Structural Dynamics During the Switching of the Photomagnetic Complex [Fe(L222 N5 )(CN)2 ].

The [Fe(L222 N5 )(CN)2 ] compound, where L222 N5 refers to the macrocyclic Schiff-base ligand, 2,13-dimethyl-3,6,9,-12,18-pentaazabicyclo[12.3.1]octadeca-1(18),2,12,14,- 16-pentaene, is a photomagnetic FeII based coordination compound, which undergoes light-induced excited spin-state trapping (LIESST). The low spin state is hexacoordinated and the high spin state heptacoordinated. This system also serves as complex for the design of trinuclear or one-dimensional compounds made of other types of bricks with diverse coordinated metals. Here its ultrafast spin-state photoswitching dynamics are studied, by combining femtosecond optical spectroscopy and femtosecond X-ray absorption measurements at the XPP station of the X-ray free-electron laser LCLS. DFT and TD-DFT calculations are used to interpret experimental findings. These studies, performed in the solution phase, show that LIESST in [Fe(L222 N5 )(CN)2 ] occurs on the 100 fs timescale under different types of photoexcitation. In addition, coherent oscillations were observed, resulting from the structural dynamics accompanying LIESST, which were recently evidenced in more conventional octahedral FeII N6 systems.

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching.

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born-Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy)3]2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersion of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.

A ZrNiAl related high-pressure modification of CeRuSn.

Monoclinic CeRuSn with its own structure type transforms to a high-pressure modification at 11.5 GPa and 1470 K (1000 t press, Walker type module). The structure of the high-pressure phase was refined from X-ray single crystal diffractometer data at room temperature. The HP-CeRuSn subcell structure adopts the ZrNiAl type: P6[combining macron]2m, a = 751.4(3) and c = 394.6(2) pm, wR2 = 0.0787, 310 F(2) values and 15 variables. The Ru2 atoms within the Sn6 trigonal prisms show a strongly enhanced U33 parameter. Weak satellite reflections indicate a commensurate modulation: (3 + 1)D superspace group P31m(1/3,1/3,γ)000, a = 751.4(3) and c = 394.6(2) pm, γ = -1/3, wR2 = 0.0786, 1584 F(2) values, 32 variables for the main reflections and wR2 = 0.3757 for the satellites of 1(st) order. A description of this new superstructure variant of the ZrNiAl type is possible in a transformed 3D supercell with the space group R3m and Z = 9. The driving force for formation of the modulation is strengthening of Ru-Sn bonding within the comparatively large Ru@Sn6 trigonal prisms. Electronic structure calculations point to an almost depleted Ce 4f shell. This is substantiated by temperature-dependent magnetic susceptibility data. Fitting of the data within the interconfiguration fluctuation model (ICF) resulted in cerium valences of 3.41 at 10 K and 3.31 at 350 K. Temperature dependent specific heat data underline the absence of magnetic ordering.

Multiscale experimental and theoretical investigations of spin crossover Fe(II) complexes: examples of [Fe(phen)2(NCS)2] and [Fe(PM-BiA)2(NCS)2].

For spin crossover (SCO) complexes, computation results are reported and confirmed with experiments at multiscale levels of the isolated molecule and extended solid on the one hand and theory on the other hand. The SCO phenomenon which characterizes organometallics based on divalent iron in an octahedral FeN6-like environment with high spin (HS) and low spin (LS) states involves the LS/HS switching at the cost of small energies provided by temperature, pressure or light, the latter connected with Light-Induced Excited Spin-State Trapping (LIESST) process. Characteristic infra red (IR) and Raman vibration frequencies are computed within density functional theory (DFT) framework. In [Fe(phen)2(NCS)2] a connection of selected frequencies is established with an ultra-fast light-induced LS → HS photoswitching mechanism. In the extended solid, density of state DOS and electron localization function (ELF) are established for both LS and HS forms, leading to characterizion of the compound as an insulator in both spin states with larger gaps for LS configuration, while keeping molecular features in the solid. In [Fe(PM-BiA)2(NCS)2], by combining DFT and classical molecular dynamics, the properties and the domains of existence of the different phases are obtained by expressing the potential energy surfaces in a short range potential for Fe-N interactions. Applying such Fe-N potentials inserted in a classical force field and carrying out molecular dynamics (MD) in so-called "semi-classical MD" calculations, lead to the relative energies of HS/LS configurations of the crystal and to the assessment of the experimental (P, T) phase diagram.

Ultrafast light-induced spin-state trapping photophysics investigated in Fe(phen)2(NCS)2 spin-crossover crystal.

Few photoactive molecules undergo a complete transformation of physical properties (magnetism, optical absorption, etc.) when irradiated with light. Such phenomena can happen on the time scale of fundamental atomic motions leading to an entirely new state within less than 1 ps following light absorption. Spin crossover (SCO) molecules are prototype systems having the ability to switch between low spin (LS) and high spin (HS) molecular states both at thermal equilibrium and after light irradiation. In the case of Fe(II) (3d(6)) complexes in a nearly octahedral ligand field, the two possible electronic distributions among the 3d split orbitals are S = 0 for the LS diamagnetic state and S = 2 for the HS paramagnetic state. In crystals, such photoexcited states can be long-lived at low temperature, as is the case for the photoinduced HS state of the [Fe(phen)2(NCS)2] SCO compound investigated here. We first show how such bistability between the diamagnetic and paramagnetic states can be characterized at thermal equilibrium or after light irradiation at low temperature. Complementary techniques provide invaluable insights into relationships between changes of electronic states and structural reorganization. But the development of such light-active materials requires the understanding of the basic mechanism following light excitation of molecules, responsible for trapping them into new electronic and structural states. We therefore discuss how we can observe a photomagnetic molecule during switching and catch on the fly electronic and structural molecular changes with ultrafast X-ray and optical absorption spectroscopies. In addition, there is a long debate regarding the mechanism behind the efficiency of such a light-induced process. Recent theoretical works suggest that such speed and efficiency are possible thanks to the instantaneous coupling with the phonons of the final state. We discuss here the first experimental proof of that statement as we observe the instantaneous activation of one key phonon mode precluding any recurrence towards the initial state. Our studies show that the structural molecular reorganization trapping the photoinduced electronic state occurs in two sequential steps: the molecule elongates first (within 170 femtosecond) and bends afterwards. This dynamics is caught via the coherent vibrational energy transfer of the two main structural modes. We discuss the transformation pathway connecting the initial photoexcited state to the final state, which involves several key reaction coordinates. These results show the need to replace the classical single coordinate picture employed so far with a more complex multidimensional energy surface.

Sequential Activation of Molecular Breathing and Bending during Spin-Crossover Photoswitching Revealed by Femtosecond Optical and X-Ray Absorption Spectroscopy.

We study the basic mechanisms allowing light to photoswitch at the molecular scale a spin-crossover material from a low- to a high-spin state. Combined femtosecond x-ray absorption performed at LCLS X-FEL and optical spectroscopy reveal that the structural stabilization of the photoinduced high-spin state results from a two step structural trapping. Molecular breathing vibrations are first activated and rapidly damped as part of the energy is sequentially transferred to molecular bending vibrations. During the photoswitching, the system follows a curved trajectory on the potential energy surface.

Drastic change of the ferromagnetic properties of the ternary germanide GdTiGe through hydrogen insertion.

Hydrogen absorption of the CeFeSi- and CeScSi-type forms of GdTiGe was performed. Before hydrogenation they show an antiferromagnetic transition at around 412 K and a ferromagnetic transition at 376 K, respectively. Hydrogenation of both forms leads to formation of the same hydride GdTiGeH which crystallizes with a filled CeScSi-type structure where all the [Gd(4)] tetrahedra are filled by hydrogen. This hydride is paramagnetic in the temperature range 4-300 K. The slightly negative value of the paramagnetic Curie temperature θ(p) confirms that all ferromagnetic interactions were destroyed in the case of the CeScSi-type form. From first-principles calculations with the PAW GGA methodology, the localization of hydrogen within the [Gd(4)] tetrahedra was confirmed through energetic stabilization. It was also seen that the energy changes significantly with volume, indicating the itinerant (delocalized) role of the electrons in the magnetism.

Hydrogenation inducing ferromagnetism in the ternary antiferromagnet NdCoSi.

The hydride NdCoSiH obtained by exposure at 523 K of the ternary antiferromagnet NdCoSi under a pressure of 4 MPa of hydrogen crystallizes in the tetragonal ZrCuSiAs-type structure where H atoms occupy the tetrahedral [Nd(4)] site. The hydrogenation induces an increase in the unit cell volume close to 6%. The investigation of NdCoSiH by magnetization measurements reveals its ferromagnetic behavior below T(C) = 20.5(5) K. Neutron powder diffraction shows that the T(C) temperature is associated with a ferromagnetic arrangement of the Nd moments (2.3(2) mu(B) at 1.5 K) parallel to the c axis as observed for NdFeSi. The magnetic properties, magnetic structure, and the value of the Nd ordered magnetic moment evidenced for NdCoSiH are discussed using both band structure calculations and a comparison with the behavior of NdCoSi and NdFeSi.