Nanophase iron (oxyhydr)oxides are ubiquitous on Earth, globally distributed on Mars, and likely present on numerous other rocky solar system bodies. They are often structurally and, therefore, spectrally distinct from iron (oxyhydr)oxide bulk phases. Because their spectra vary with grain size, they can be difficult to identify or distinguish unless multiple analysis techniques are used in tandem. Yet, most literature reports fail to use multiple techniques or adequately parameterize sample morphology, making it difficult to understand how morphology affects spectral characteristics across techniques. Here, we present transmission electron microscopy, Raman, visible and near-infrared, and mid-infrared attenuated total reflectance data on synthetic, nanophase akaganéite, lepidocrocite, goethite, hematite, ferrihydrite, magnetite, and maghemite. Feature positions are tabulated and compared to those for bulk (oxyhydr)oxides and other nanophase iron (oxyhydr)oxides from the literature. The utility and limitations of each technique in analyzing nanophase iron (oxyhydr)oxides are discussed. Raman, mid-infrared, and visible near-infrared spectra show broadening, loss of some spectral features, and shifted positions compared to bulk phases. Raman and mid-infrared spectroscopies are useful in identifying and distinguishing akaganéite, lepidocrocite, goethite, and hematite, though ferrihydrite, magnetite, and maghemite have overlapped band positions. Visible near-infrared spectroscopy can identify and distinguish among ferrihydrite, magnetite, and maghemite in pure spectra, though akaganéite, lepidocrocite, and goethite can have overlapping bands. It is clear from this work that further understanding of variable spectral features in nanophase iron (oxyhydr)oxides must await additional studies to robustly assess effects of morphology. This study establishes a template for future work.

Lamellae of 1.5 µm thickness, prepared from well-crystallised monazite-(Ce) and zircon samples using the focused-ion-beam technique, were subjected to triple irradiation with 1 MeV Au ions (15.6% of the respective total fluence), 4 MeV Au ions (21.9%) and 10 MeV Au ions (62.5%). Total irradiation fluences were varied in the range 4.5 × 10 - 1.2 × 10 ions/cm. The highest fluence resulted in amorphisation of both minerals; all other irradiations (i.e. up to 4.5 × 10 ions/cm) resulted in moderate to severe damage. Lamellae were subjected to Raman and laser-induced photoluminescence analysis, in order to provide a means of quantifying irradiation effects using these two micro-spectroscopy techniques. Based on extensive Monte Carlo calculations and subsequent defect-density estimates, irradiation-induced spectroscopic changes are compared with those of naturally self-irradiated samples. The finding that ion irradiation of monazite-(Ce) may cause severe damage or even amorphisation, is in apparent contrast to the general observation that naturally self-irradiated monazite-(Ce) does not become metamict (i.e. irradiation-amorphised), in spite of high self-irradiation doses. This is predominantly assigned to the continuous low-temperature damage annealing undergone by this mineral; other possible causes are discussed. According to cautious estimates, monazite-(Ce) samples of Mesoproterozoic to Cretaceous ages have stored only about 1% of the total damage experienced. In contrast, damage in ion-irradiated and naturally self-irradiated zircon is on the same order; reasons for the observed slight differences are discussed. We may assess that in zircon, alpha decays create significantly less than 10 Frenkel-type defect pairs per event, which is much lower than previous estimates. Amorphisation occurs at defect densities of about 0.10 dpa (displacements per lattice atom).

The chemically driven propagation of interacting parallel cracks in monoclinic alkali feldspar was studied experimentally. Single crystals of potassium-rich gem-quality sanidine were shifted towards more sodium-rich compositions by cation exchange with a NaCl-KCl salt melt at a temperature of and close to ambient pressure. Initially, a zone with elevated sodium content formed at the crystal surfaces due to the simultaneous in-diffusion of sodium and out-diffusion of potassium, where the rate of cation exchange was controlled by sodium-potassium interdiffusion within the feldspar. A chemical shift of potassium-rich alkali feldspar towards more sodium-rich compositions produces highly anisotropic contraction of the crystal lattice. This induced a tensile stress state in the sodium-rich surface layer of the crystals, which triggered the formation of a system of nearly equi-spaced parallel cracks oriented approximately perpendicular to the direction of maximum shortening. Crack propagation following their nucleation was driven by cation exchange occurring along the crack flanks and was controlled by the intimate coupling of the diffusion-mediated build-up of a tensile stress state around the crack tips and stress release by successive crack propagation. The critical energy release rate of fracturing was determined as 1.8-2.2 from evaluation of the near-tip J-integral. The mechanism of diffusion-controlled crack propagation is discussed in the context of high-temperature feldspar alteration.

Calculations using the density-functional theory (DFT) in combination with the single defect method were carried out to determine the heat of mixing behaviour of mineral solid solution phases. The accuracy of this method was tested on the halite-sylvite (NaCl-KCl) binary, pyrope-grossular garnets (MgAlSiO-CaAlSiO), MgO-CaO (halite structure) binary, and on Al/Si ordered alkali feldspars (NaAlSiO-KAlSiO); as members for coupled substitutions, the diopside-jadeite pyroxenes (CaMgSiO-NaAlSiO) and diopside-CaTs pyroxenes (CaMgSiO-CaAlAlSiO) were chosen for testing and, as an application, the heat of mixing of the tremolite-glaucophane amphiboles (CaMgSiO(OH)-NaMgAlSiO(OH)) was computed. Six of these binaries were selected because of their experimentally well-known thermodynamic mixing behaviours. The comparison of the calculated heat of mixing data with calorimetric data showed good agreement for halite-sylvite, pyrope-grossular, and diopside-jadeite binaries and small differences for the Al/Si ordered alkali feldspar solid solution. In the case of the diopside-CaTs binary, the situation is more complex because CaTs is an endmember with disordered cation distributions. Good agreement with the experimental data could be, however, achieved assuming a reasonable disordered state. The calculated data for the Al/Si ordered alkali feldspars were applied to phase equilibrium calculations, i.e. calculating the Al/Si ordered alkali feldspar solvus. This solvus was then compared to the experimentally determined solvus finding good agreement. The solvus of the MgO-CaO binary was also constructed from DFT-based data and compared to the experimentally determined solvus, and the two were also in good agreement. Another application was the determination of the solvus in tremolite-glaucophane amphiboles (CaMgSiO(OH)-NaMgAlSiO(OH)). It was compared to solvi based on coexisting amphiboles found in eclogites and phase equilibrium experiments.

In this study, we present the first systematic dataset on natural variations of OH defect and trace element contents in quartz within igneous bodies. Samples were derived from bore holes of two plutonic bodies from the Krušné Hory/Erzgebirge (German-Czech border), representing typical A-type (Cínovec/Zinnwald granite cupola) and S-type (Podlesí Stock) granite intrusions. Fourier Transform Infrared spectroscopy of quartz was used to investigate the sample set with regard to its OH defect speciation and content. For Zinnwald quartz, IR absorption spectra reveal different lithologies due to changes of the OH defect inventory, enabling a subdivision of the granitic body: (1) hydrothermal greisen quartz of the uppermost part of the intrusion have low OH defect contents (average of 15 µg/g HO); (2) zinnwaldite granite quartz vary strongly in defect content and show the highest content of the dataset (10-70 µg/g HO); (3) quartz from an underlying biotite granite have slightly lower, but very uniform contents down to the bottom of the borehole at 1600 m (average 20 µg/g HO). Infrared spectra of Podlesí quartz reveal a gradual increase in total defect water content with increasing depth over 350 m (30-55 µg/g HO). Lithium contents in quartz samples from the uppermost part of the Zinnwald intrusion correlate with the occurrence of Li-specific OH defects, while cathodoluminescence (CL) images do not show specific differences. Our findings evidence the potential of OH defects in quartz as a tool to decipher differentiation trends in igneous bodies, and the application of their eroded material for provenance analyses.

The cations of an ordered omphacite from the Tauern window were gradually disordered in piston cylinder experiments at temperatures between 850 and 1150 °C. The samples were examined by X-ray powder diffraction and then investigated using low-temperature calorimetry and IR spectroscopy. The low-temperature heat capacity data were used to obtain the vibrational entropies, and the line broadening of the IR spectra served as a tool to investigate the disordering enthalpy. These data were then used to calculate the configurational entropy as a function of temperature. The vibrational entropy does not change during the cation ordering phase transition from space group to at 865 °C but increases with a further temperature increase due to the reduction of short-range order.

The Fe-Ni-Si system is potentially a very important component of terrestrial planetary cores. However, at present, even the behaviour of the FeSi and NiSi end members is poorly understood, especially at low to moderate pressures-the data for FeSi are contradictory and NiSi has been little studied. For FeSi, there is general agreement that there is a phase transition from the ε-FeSi to the CsCl structure with increasing pressure, but, in experiments, there is disagreement as to the position and slope of the phase boundary and the range of coexistence of the two phases. In this paper we have used lattice dynamics calculations to determine the phase boundary between the ε-FeSi and CsCl structures as a function of pressure and temperature in both FeSi and NiSi. For FeSi, we find that the transition pressure at zero Kelvin is ~11 GPa and that the boundary between the ε-FeSi and CsCl phases varies little with temperature, having a slight negative Clapeyron slope, going from ~11 GPa at 300 K to ~3 GPa at 2000 K. For NiSi, there is much greater variation of the transition pressure with temperature, with a much shallower negative Clapeyron slope, going from ~156 GPa at 300 K to ~94 GPa at 2000 K.

Starting from a synthetic sample with composition Al(SO)·16.6HO, the high-temperature- and moisture-dependent behavior of alunogen has been unraveled by TGA measurements, in situ powder X-ray diffraction as well as by gravimetric moisture sorption/desorption studies. Heating experiments using the different techniques show that alunogen undergoes a first dehydration process already starting at temperatures slightly above 40 °C. The crystalline product of the temperature-induced dehydration corresponds to the synthetic equivalent of meta-alunogen and has the following chemical composition: Al(SO)·13.8HO or Al(SO)(HO)·1.8HO. At 90 °C a further reaction can be monitored resulting in the formation of an X-ray amorphous material. The sequence of "amorphous humps" in the patterns persists up to 250 °C, where a re-crystallization process is indicated by a sudden appearance of a larger number of sharp Bragg peaks. Phase analysis confirmed this compound to be anhydrous Al(SO). Furthermore, meta-alunogen can be also obtained from alunogen at room temperature when stored at relative humidities (RH) lower than 20 %. The transformation is reversible, however, water sorption of meta-alunogen to alunogen and the corresponding desorption reaction show considerable hysteresis. For RH values above 80 %, deliquescence of the material was observed. Structural investigations on meta-alunogen were performed using a sample that has been stored at dry conditions (0 % RH) over phosphorus pentoxide. Powder diffraction data were acquired on an in-house high-resolution diffractometer in transmission mode using a sealed glass capillary as sample holder. Indexing resulted in a triclinic unit cell with the following lattice parameters:  = 14.353(6) Å,  = 12.490(6) Å,  = 6.092(3) Å,  = 92.656(1)°,  = 96.654(1)°,  = 100.831(1)°,  = 1062.8(8) Å and  = 2. These data correct earlier findings suggesting an orthorhombic cell. Ab-initio structure solution in space group [Formula: see text], using simulated annealing, provided a chemically meaningful structure model. The asymmetric unit of meta-alunogen contains three symmetry independent SO-tetrahedra and two Al(HO) octahedra. The polyhedra are isolated, however, linkage between them is provided by Coulomb interactions and hydrogen bonding. In addition to the water molecules which directly belong to the coordination environment of the aluminum cations there are two additional zeolitic water sites (Ow1 and Ow2). If both positions are fully occupied meta-alunogen corresponds to a 14-hydrate. Structural similarities and differences between the previously unknown structure of meta-alunogen and alunogen are discussed in detail. Since hydrous aluminum sulfates have been postulated to occur in Martian soils, our results may help identifying meta-alunogen by X-ray diffraction not only on the surface of the Earth but also using the Curiosity Rover's ChemMin instrument.

Zeolites show remarkable properties that can be tuned through cation exchange of their original extraframework content. In this respect, the response of the modified zeolite to the heating stimuli, in terms of structural modifications and thermal stability, can drastically change and is, therefore, an important factor to consider. In this study, the dehydration mechanism of a natural levyne previously exchanged with Cd has been monitored in situ by single crystal X-ray diffraction. The initial dehydration trend between 50 and 175 °C is similar to that observed for the pristine material, levyne-Ca. The water loss is accompanied by extraframework cation migration within the zeolitic cavities and the unit-cell volume slightly contracts from 3503.8(1) to 3467.8(6) Å. From 200 to 250 °C, a pronounced drop of the unit-cell volume (- 7%) is observed. The dehydrated structure at 250 °C corresponds to levyne B topology of natural levyne, characterized by the statistical rupture of the T-O-T bonds of the double six-ring membered cage. However, in contrast to levyne-Ca, the fraction of broken connections reached 50% instead of 37%, and no additional structural modifications were detected up to 350 °C. At 400 °C, diffraction data pointed to the onset of the structural collapse. At this temperature, the measured unit-cell volume was 8% smaller compared to that of the RT structure. The corresponding contracted structure did not rehydrate after exposure to humid conditions for 21 days.

The heat capacity, , of synthetic hydroxyapatite [Ca(PO)OH-OH-Ap], as well as of ten compositions along the OH-Ap-chlorapatite (Cl-Ap) join and 12 compositions along the OH-Ap-fluorapatite (F-Ap) join have been measured using relaxation calorimetry (heat capacity option of the Physical Properties Measurement System-PPMS) and differential scanning calorimetry (DSC) in the temperature range of 5-764 K. Apatites along the Cl-OH and F-OH joins were synthesized at 1100 °C and 300 MPa in an internally heated gas pressure vessel via an exchange process between synthetic fluorapatite or chlorapatite crystals (200-500 μm size) and a series of Ca(OH)-HO solutions with specific compositions and amounts relative to the starting apatite. The standard third-law entropy of OH-Ap, derived from the low-temperature heat capacity measurements, is ° = 386.3 ± 2.5 J mol K, which is ~ 1% lower than that resulting from low-temperature adiabatic calorimetry data on OH-Ap from the 1950's. The heat capacity of OH-Ap above 298.15 K shows a hump-shaped anomaly centred around 442 K. Based on published structural and calorimetric work, this feature is interpreted to result from a monoclinic to hexagonal phase transition. Super ambient up to this transition can be represented by the polynomial: . The DSC data above this transition were combined with heat capacities computed using density functional theory and can be given by the polynomial: . Positive excess heat capacities of mixing, ∆ , in the order of 1-2 J mol K, occur in both solid solutions at around 70 K. They are significant at these conditions exceeding the 2σ-uncertainty of the data. This positive ∆ is compensated by a negative ∆ of the same order at around 250 K in both binaries. At higher temperatures (up to 1200 K), ∆ is zero within error for all solid solution members. As a consequence, the calorimetric entropies, S, show no deviation from ideal mixing behaviour within a 2σ-uncertainty for both joins. Excess entropies of mixing, ∆S, are thus zero for the OH-Ap-F-Ap, as well as for the OH-Ap-Cl-Ap join. The - behaviour of the OH-Ap endmember is discussed in relation to that of the F- and Cl-endmembers.

Five different interatomic potentials designed for modelling forsterite Mg SiO are compared to and experimental data. The set of tested properties include lattice constants, material density, elastic wave velocity, elastic stiffness tensor, free surface energies, generalized stacking faults, neutral Frenkel and Schottky defects, in the pressure range  GPa relevant to the Earth's upper mantle. We conclude that all interatomic potentials are reliable and applicable to the study of point defects. Stacking faults are correctly described by the THB1 potential, and qualitatively by the Pedone2006 potential. Other rigid-ion potentials give a poor account of stacking fault energies, and should not be used to model planar defects or dislocations. These results constitute a database on the transferability of rigid-ion potentials, and provide strong physical ground for simulating diffusion, dislocations, or grain boundaries.

A system of edge cracks was applied to polished (010) surfaces of K-rich gem-quality alkali feldspar by diffusion-mediated cation exchange between oriented feldspar plates and a Na-rich NaCl-KCl salt melt. The cation exchange produced a Na-rich layer at and beneath the specimen surface, and the associated strongly anisotropic lattice contraction lead to a tensile stress state at the specimen surface, which induced fracturing. Cation exchange along the newly formed crack flanks produced Na-enriched diffusion halos around the cracks, and the associated lattice contraction and tensile stress state caused continuous crack growth. The cracks nucleated with non-uniform spacing on the sample surface and quickly attained nearly uniform spacing below the surface by systematic turning along their early propagation paths. In places, conspicuous wavy cracks oscillating several times before attaining their final position between the neighboring cracks were produced. It is shown that the evolution of irregularly spaced towards regularly spaced cracks including the systematic turning and wavyness along the early propagation paths maximizes the rate of free energy dissipation in every evolutionary stage of the system. Maximization of the dissipation rate is suggested as a criterion for selection of the most probable evolution path for a system undergoing chemically induced diffusion mediated fracturing in an anisotropic homogeneous brittle material.

The ultimate mechanical properties of MgSiO orthoenstatite (OEN), as characterized here by the ideal strengths, have been calculated under tensile and shear loadings using first-principles calculations. Both ideal tensile strength (ITS) and shear strength (ISS) are computed by applying homogeneous strain increments along high-symmetry directions ([100], [010], and [001]) and low index shear planes ((100), (010), and (001)) of the orthorhombic lattice. We show that the ultimate mechanical properties of OEN are highly anisotropic during tensile loading, with ITS ranging from 4.5 GPa along [001] to 8.7 GPa along [100], and quite isotropic during the shear loading with ISS ranging from 7.4 to 8.9 GPa. During tensile test along [100] and [001], a modified structure close to OEN has been found. This modified structure is more stable than OEN under stress (or strain). We have characterized its elastic and ultimate properties under tensile loading. With ITS ranging from 7.6 GPa along [010] to 25.6 GPa along [001], this modified structure appears to be very anisotropic with exceptional strength along [001].

High-Pressure Collaborative Access Team (HPCAT) is a synchrotron-based facility located at the Advanced Photon Source (APS). With four online experimental stations and various offline capabilities, HPCAT is focused on providing synchrotron x-ray capabilities for high pressure and temperature research and supporting a broad user community. Overall, the array of online/offline capabilities is described, including some of the recent developments for remote user support and the concomitant impact of the current pandemic. General overview of work done at HPCAT and with a focus on some of the minerals relevant work and supporting capabilities is also discussed. With the impending APS-Upgrade (APS-U), there is a considerable effort within HPCAT to improve and add capabilities. These are summarized briefly for each of the end-stations.

Experimentally, silica activity (aSiO) has been shown to have an effect on Mg diffusion in forsterite, but no fully satisfactory mechanism has yet been proposed. We calculated the effects of aSiO and aluminium content (the main contaminant in some recent experimental studies), and their co-effect, on Mg diffusion in forsterite, using thermodynamic minimisations of defect formation energies [calculated using density functional theory (DFT)] and a Monte-Carlo diffusion model. These two variables, in isolation, do not appreciably change the defect concentrations of forsterite and thus do not affect the diffusivity of Mg. However, when elevated together, they cause large increases in the Mg vacancy content and thus can increase the Mg diffusivity by one to six orders of magnitude depending on temperature, with little pressure dependence. This effect is largely independent of AlO concentration above ~ 1 wt. ppm, and thus, for all practical purposes, should occur wherever forsterite is in the presence of enstatite. It is also largely dependent upon configurational entropy and is thus highly sensitive to the chemistry of the crystal. A low concentration of structurally bound hydroxyl groups at low temperatures (1000 K) suppresses this effect in pure forsterite, but it is likely robust in the presence of water either when alternative water sinks (such as Ti or Fe) are present, or at high temperatures (> 1500 K). This effect is also robust in the presence of ferrous iron (or other substitutional Mg defects) at all temperatures. FeO can operate like AlO in this reaction and should enhance its effect. These findings explain the experimentally observed dependency of Mg diffusion of aSiO, and elucidate how chemical activity variations in both experiments and natural settings could affect not only the diffusivity of Mg in forsterite, but of olivine-hosted cations in general.

ABF compounds have been found to make valuable low-pressure analogues for high-pressure silicate phases that are present in the Earth's deep interior and that may also occur in the interiors of exoplanets. The phase diagrams of two of these materials, KCaF and NaMgF, have been investigated in detail by static ab initio computer simulations based on density functional theory. Six ABF polymorphs were considered, as follows: the orthorhombic perovskite structure (GdFeO-type; space group ); the orthorhombic CaIrO structure (; commonly referred to as the "post-perovskite" structure); the orthorhombic SbS and LaS structures (both ); the hexagonal structure previously suggested in computer simulations of NaMgF (6/); the monoclinic structure found to be intermediate between the perovskite and CaIrO structures in CaRhO (2/). Volumetric and axial equations of state of all phases considered are presented. For KCaF, as expected, the perovskite phase is shown to be the most thermodynamically stable at atmospheric pressure. With increasing pressure, the relative stability of the KCaF phases then follows the sequence: perovskite → LaS structure → SbS structure → 6/ structure; the CaIrO structure is never the most stable form. Above about 2.6 GPa, however, none of the KCaF polymorphs are stable with respect to dissociation into KF and CaF. The possibility that high-pressure KCaF polymorphs might exist metastably at 300 K, or might be stabilised by chemical substitution so as to occur within the standard operating range of a multi-anvil press, is briefly discussed. For NaMgF, the transitions to the high-pressure phases occur at pressures outside the normal range of a multi-anvil press. Two different sequences of transitions had previously been suggested from computer simulations. With increasing pressure, we find that the relative stability of the NaMgF phases follows the sequence: perovskite → CaIrO structure → SbS structure → 6/ structure. However, only the perovskite and CaIrO structures are stable with respect to dissociation into NaF and MgF.

We present a model for multicomponent diffusion in ionic crystals. The model accounts for vacancy-mediated diffusion on a sub-lattice and for diffusion due to binary exchange of different ionic species without involvement of vacancies on the same sub-lattice. The diffusive flux of a specific ionic species depends on the self-diffusion coefficients, on the diffusion coefficients related to the binary exchanges, and on the site fractions of all ionic species. The model delivers explicit expressions for these dependencies, which lead to a set of coupled non-linear diffusion equations. We applied the model to diffusion of Na, K, and K in alkali feldspar. To this end, gem-quality crystals of alkali feldspar were used together with K doped KCl salt as diffusion couples, which were annealed at temperatures between 800 and 950 C. Concentration-distance data for Na, K, and K were obtained by Time of Flight Secondary Ion Mass Spectrometry. Over the entire investigated temperature range the Na self-diffusion coefficient is by a factor of higher than the K self-diffusion coefficient. Diffusion mediated by binary K- K exchange is required for obtaining satisfactory fits of the model curves to the experimental data, and the respective kinetic coefficient is well constrained.

In this study, we investigate the complex structure of [001] screw and edge dislocation cores in MgSiO post-perovskite at the atomic scale. Both [001] screw and edge dislocations exhibit spontaneous dissociation in (010) into two symmetric partials characterized by the presence of <100> component. In case of edge dislocations, dissociation occurs into ½<101> partials, while for the screw dislocations the <100> component reaches only 15%. Under applied stress, both [001](010) screw and edge dislocations behave similarly. Above the Peierls stress, the two partials glide together while keeping their stacking-fault widths (~11 and ~42 Å for the screw and edge dislocations, respectively) constant. The Peierls stress opposed to the glide of [001](010) screw dislocations is 3 GPa, while that of edge dislocations is 33% lower. Relying on the observed characteristics of the dislocation cores, we estimate the efficiency of [001](010) dislocation glide under the - conditions relevant to the lowermost mantle and demonstrate that dislocation creep for this slip system would occur in the so-called athermal regime where lattice friction for the considered slip system vanishes when the temperature rises above the critical value of ~2,000 K.

We used atom probe tomography to complement electron microscopy for the investigation of spinodal decomposition in alkali feldspar. To this end, gem-quality alkali feldspar of intermediate composition with a mole fraction of of the K end-member was prepared from Madagascar orthoclase by ion-exchange with (NaK)Cl molten salt. During subsequent annealing at and close to ambient pressure the ion-exchanged orthoclase unmixed producing a coherent lamellar intergrowth of Na-rich and K-rich lamellae. The chemical separation was completed, and equilibrium Na-K partitioning between the different lamellae was attained within four days, which was followed by microstructural coarsening. After annealing for 4 days, the wavelength of the lamellar microstructure was and it increased to after annealing for 16 days. The observed equilibrium compositions of the Na-rich and K-rich lamellae are in reasonable agreement with an earlier experimental determination of the coherent solvus. The excess energy associated with compositional gradients at the lamellar interfaces was quantified from the initial wavelength of the lamellar microstructure and the lamellar compositions as obtained from atom probe tomography using the Cahn-Hilliard theory. The capability of atom probe tomography to deliver quantitative chemical compositions at nm resolution opens new perspectives for studying the early stages of exsolution. In particular, it helps to shed light on the phase relations in nm scaled coherent intergrowth.

In this study, we propose a full atomistic study of [100] dislocations in MgSiO post-perovskite based on the pairwise potential parameterized by Oganov et al. (Phys Earth Planet Inter 122:277-288, 2000) for MgSiO perovskite. We model screw dislocations to identify planes where they glide easier. We show that despite a small tendency to core spreading in {011}, [100] screw dislocations glide very easily (Peierls stress of 1 GPa) in (010) where only Mg-O bonds are to be sheared. Crossing the Si-layers results in a higher lattice friction as shown by the Peierls stress of [100](001): 17.5 GPa. Glide of [100] screw dislocations in {011} appears also to be highly unfavorable. Whatever the planes, (010), (001) or {011}, edge dislocations are characterized by a wider core (of the order of 2). Contrary to screw character, they bear negligible lattice friction (0.1 GPa) for each slip system. The layered structure of post-perovskite results in a drastic reduction in lattice friction opposed to the easiest slip systems compared to perovskite.

The heat of mixing of some petrological relevant substitutions (i.e., Mg-Al, Si-Al, Mg-Ti, Mg-Ca, and Mg-Fe) was investigated systematically in silicates, titanates, tungstates, carbonates, oxides, hydroxides, and sulphates by density functional theory calculations (e.g., melilite, chlorite, biotite, brucite, cordierite, amphibole, talc, pseudobrookite, pyroxene, olivine, wadsleyite, ilmenite, MgWO, ringwoodite (spinel), perovskite, pyrope-grossular, magnesite-calcite, MgO-CaO, anhydrous and different hydrated MgSO). A specific substitution is characterised by different microscopic interaction energies in different minerals, e.g., the octahedral Mg-Al exchange on a single crystallographic site in pyroxene has a microscopic interaction energy that is more than twice compared to that in biotite. A comparative investigation of the heat of mixing using microscopic interaction energies on a single crystallographic site has the advantage that they are not influenced by cation ordering. They could be successfully correlated with the stiffnesses of the minerals, which in turn were scaled to the oxygen packing fraction, a parameter that is easily available for poorly investigated minerals. With this information, the interaction energies of a certain substitution can be transferred from minerals where they are well-known to mineral groups where they are less- or unknown. Using the cross-site terms and the microscopic interaction energies, the macroscopic interaction energies of the coupled substitution, e.g., Mg + Si = Al + Al, of biotite and pyroxene were calculated, which are, however, affected by cation ordering and different degrees of local charge balance, for which appropriate models are necessary.