High-pressure Single-crystal X-ray Diffraction Research Articles

Structural insight into piezo-solvatochromism of Reichardt's dye.

To date, accurate modelling of the solvation process is challenging, often over-simplifying the solvent-solute interactions. The interplay between the molecular arrangement associated with the solvation process and crystal nucleation has been investigated by analysis of the piezo-solvatochromic behaviour of Reichardt's dye, ET(1), in methanol, ethanol and acetone under high pressure. High-pressure single-crystal X-ray diffraction and UV-Vis spectroscopy reveal the impact of solute-solvent interactions on the optical properties of ET(1). The study underscores the intricate relationship between solvent properties, molecular conformation and crystal packing. The connection between liquid and solid phases emphasizes the capabilities of high-pressure methods for expanding the field of crystal engineering. The high-pressure environment allowed the determination of the crystal structures reported here that are built from organic molecules fourfold solvated with ethanol or methanol: ET(1)·4CH3OH and ET(1)·4C2H5OH·H2O. The observed piezo-solvatochromic effects highlight the potential of ET(1) in nonlinear optoelectronics and expand the application of solvatochromic chemical indicators to pressure sensors.

High-Pressure Structural and Optical Studies of Pure Low-Dimensional Cesium Lead Chlorides CsPb2Cl5 and Cs4PbCl6.

We report high-pressure single-crystal X-ray diffraction, optical absorption, and photoluminescence investigations of all-inorganic perovskite-related materials CsPb2Cl5 and Cs4PbCl6. The crystal structure of CsPb2Cl5, composed of alternate layers of Cs+ cations and Pb-Cl frameworks, is stable under pressure up to at least 4.2 GPa. Because external stress is mainly absorbed by the Cs+ layers, the optical absorption edge of the crystal only slightly red-shifts with increasing pressure, which correlates well with a moderate shortening of the Pb-Cl bonds. A quite different response to pressure shows Cs4PbCl6, the crystal built of isolated PbCl64- octahedra and Cs+ cations. During the compression at around 3.4 GPa, the trigonal phase I, space group R3̅c, transforms to the orthorhombic phase II, space group Cmce, which at around 4 GPa transforms into phase III. On decompression, phase II is not restored, but phase III converts through a diffuse phase transition into another high-pressure phase IV, which is stable in a wide pressure range and transforms to the initial phase I only around atmospheric pressure. The red shift of the absorption edge and the profound modification of the absorption spectrum in phase II were ascribed to the deformation of the PbCl64- octahedra. The transition to phase III induces a blue shift of the absorption edge, while the transition to phase IV is associated with a large red shift. Photoluminescence was detected in phases I and II with the intensity quenched with increasing pressure.

High-pressure high-temperature synthesis of NdRe2.

In this study, we report the synthesis of a new cubic neodymium-rhenium metallic alloy NdRe2 through the utilization of high pressure and laser heating in a diamond anvil cell. NdRe2 crystallizes in the space group with a lattice parameter equal to 7.486 (2) Å and Z = 8at 24 (1) GPa and 2,200 (100) K. It was studied using high-pressure single-crystal X-ray diffraction. The compound crystallizes in the cubic MgCu2 structure type. Its successful synthesis further proves that high-pressure high-temperature conditions can be used to obtain alloys holding a Laves phase structure. Ab initio calculations were done to predict the mechanical properties of the material. We also discuss the usage of extreme conditions to synthesize and study materials present in the nuclear waste.

Stabilization of N6 and N8 anionic units and 2D polynitrogen layers in high-pressure scandium polynitrides

Nitrogen catenation under high pressure leads to the formation of polynitrogen compounds with potentially unique properties. The exploration of the entire spectrum of poly- and oligo-nitrogen moieties is still in its earliest stages. Here, we report on four novel scandium nitrides, Sc2N6, Sc2N8, ScN5, and Sc4N3, synthesized by direct reaction between yttrium and nitrogen at 78-125 GPa and 2500 K in laser-heated diamond anvil cells. High-pressure synchrotron single-crystal X-ray diffraction reveals that in the crystal structures of the nitrogen-rich Sc2N6, Sc2N8, and ScN5 phases nitrogen is catenated forming previously unknown N66− and N86− units and ∞2(N53−)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\!\\,}_{\\infty }{\\!\\,}^{2}({{{{{\\rm{N}}}}}}_{5}^{3-})$$\\end{document} anionic corrugated 2D-polynitrogen layers consisting of fused N12 rings. Density functional theory calculations, confirming the dynamical stability of the synthesized compounds, show that Sc2N6 and Sc2N8 possess an anion-driven metallicity, while ScN5 is an indirect semiconductor. Sc2N6, Sc2N8, and ScN5 solids are promising high-energy-density materials with calculated volumetric energy density, detonation velocity, and detonation pressure higher than those of TNT.

The crystal structure of hexaphenylbenzene under high hydrostatic pressure

High-pressure single-crystal X-ray diffraction, intermolecular interaction energy calculations, and density functional theory are used to examine the structure and emission properties of hexaphenylbenzene during hydrostatic compression to 4.14 GPa.

Negative linear compressibility and strong enhancement of emission in Eu[Ag(CN)2]3·3H2O under pressure.

The framework material Eu[Ag(CN)2]3·3H2O exhibits a negative linear compressibility (NLC) of -4.2(1) TPa-1 over the largest pressure range yet observed (0-8.2 GPa). High-pressure single-crystal X-ray diffraction data show that the rapid contraction of the Kagome silver layers under compression causes the wine-rack lattice to expand along the c-axis. The hydrogen bonds between the water molecules and the main frameworks constrain the structural deformation under pressure and eventually a weak NLC effect generated. Furthermore, we found that the pressure-induced emission intensity increases almost 800-fold at 4.0 GPa, followed by a gradual decrease and disappearance at 8.1 GPa. Under compression, high pressure significantly tunes the triplet level positions near the Eu3+ ions, and horizontal displacement between a quenching excited state and the excited levels of Eu3+ facilitates the energy transfer process to the 5D0 excited state and limits the nonradiative corssover at elevated pressures, thus increasing the emission intensity. In addition, we observe a gradual band gap reduction with increasing pressure, and the sample could not be returned to the initial state after the pressure was completely released. By controlling the structural flexibility, we observe a coupled NLC and pressure-induced strong enhancement of the emission properties of Eu[Ag(CN)2]3·3H2O, which provides a new route for the design of new optical devices with intriguing luminescence properties under extreme environments.

Pressure-Induced Coordination Number Transition in Lanthanide Mellitate Coordination Polymers: Structure and Spectroscopy.

High external pressure is found to induce a non-coordinated water molecule to bond to cerium in a previously studied mellitate coordination polymer, as determined by high-pressure single-crystal X-ray diffraction, resulting in a coordination number transition at 3.85 GPa from 9 to 9.5 where half the cerium ions are 10-coordinate. Also, bond length changes due to increased pressure are experimentally measured, whereas the cerium-carboxylate bond lengths overall change by -0.004(9) Å/GPa, the cerium-water bonds by -0.016(3) Å/GPa, and cerium-oxygen bonds overall by -0.010(6) Å/GPa, which corresponds well with theoretical bond length decreases determined for similar compounds. The high-pressure absorbance spectra of the analogous neodymium mellitate are examined and compared with the structural changes observed.

Tandem High-Pressure Crystallography-Optical Spectroscopy Unpacks Noncovalent Interactions of Piezochromic Fluorescent Molecular Rotors.

To develop luminescent molecular materials with predictable and stimuli-responsive emission, it is necessary to correlate changes in their geometries, packing structures, and noncovalent interactions with the associated changes in their optical properties. Here, we demonstrate that high-pressure single-crystal X-ray diffraction can be combined with high-pressure UV-visible absorption and fluorescence emission spectroscopies to elucidate how subtle changes in structure influence optical outputs. A piezochromic aggregation-induced emitter, sym-heptaphenylcycloheptatriene (Ph7C7H), displays bathochromic shifts in its absorption and emission spectra at high pressure. Parallel X-ray measurements identify the pressure-induced changes in specific phenyl-phenyl interactions responsible for the piezochromism. Pairs of phenyl rings from neighboring molecules approach the geometry of a stable benzene dimer, while conformational changes alter intramolecular phenyl-phenyl interactions correlated with a relaxed excited state. This tandem crystallographic and spectroscopic analysis provides insights into how subtle structural changes relate to the photophysical properties of Ph7C7H and could be applied to a library of similar compounds to provide general structure-property relationships in fluorescent organic molecules with rotor-like geometries.

Effect of nonhydrostatic pressure on the superconducting kagome metal CsV3Sb5

High-pressure single-crystal x-ray diffraction experiments reveal that the superconducting kagome metal ${\mathrm{CsV}}_{3}{\mathrm{Sb}}_{5}$ transforms from hexagonal ($P6/mmm$) to monoclinic ($C2/m$) symmetry above 10 GPa if nonhydrostatic pressure conditions are created in a diamond anvil cell with silicon oil as the pressure-transmitting medium. This is contrary to the behavior of ${\mathrm{CsV}}_{3}{\mathrm{Sb}}_{5}$ under quasihydrostatic conditions in neon, with the hexagonal symmetry retained up to at least 20 GPa. Monoclinic distortion leaves the kagome planes almost unchanged, but deforms honeycomb nets of the Sb atoms. While the onset of the distortion almost coincides with the reentrance of superconductivity, our ab initio density-functional calculations reveal only minor changes in the electronic structure compared to the quasihydrostatic case. In particular, Fermi surface reconstruction driven by the formation of interlayer Sb-Sb bonds is observed in both monoclinic and hexagonal ${\mathrm{CsV}}_{3}{\mathrm{Sb}}_{5}$ structures at high pressures and comes out as the likely cause for the reentrant behavior.

Pressure-Induced Ferroelastic Transition Drives a Large Shape Change in a Ni(II) Complex Single Crystal.

Crystals with significant length reduction at an accessible low pressure are highly desirable for piezo-responsive devices. Here, we show a molecular crystal [Ni(en)3](ox) (en = ethylenediamine and ox = oxalate anion) that exhibits an abrupt shape change with a contraction rate of ∼4.7% along its c axis near the phase transition pressure of ∼0.2 GPa. High-pressure single-crystal X-ray diffraction and Raman spectroscopy measurements reveal that this material undergoes a first-order ferroelastic transition from high-symmetry trigonal P3̅1c to low-symmetry monoclinic P21/n at ∼0.2 GPa. The oxalate anions serve as unique components, and their disorder-order transformation and rotation of 90° through cooperative intermolecular hydrogen bonding triggered unconventional anisotropic microsize contraction under compression, which can be appreciated visually. Such a prominent directional deformation at a low pressure driven by molecular motors of oxalate anions provides insights for the design of novel molecular crystal-based piezo-responsive switches and actuators in deep-sea environments.

Structural and Luminescence Properties of Cu(I)X-Quinoxaline under High Pressure (X = Br, I)

A study of high-pressure single-crystal X-ray diffraction and luminescence experiments together with ab initio simulations based on the density functional theory has been performed for two isomorphous copper(I) halide compounds with the empirical formula [C8H6Cu2X2N2] (X = Br, I) up to 4.62(4) and 7.00(4) GPa for X-ray diffraction and 6.3(4) and 11.6(4) GPa for luminescence, respectively. An exhaustive study of compressibility has been completed by means of determination of the isothermal equations of state and structural changes with pressure at room temperature, giving bulk moduli of K0 = 14.4(5) GPa and K′0 = 7.7(6) for the bromide compound and K0 = 13.0(2) GPa and K′0 = 7.4(2) for the iodide compound. Both cases exhibited a phase transition of second order around 3.3 GPa that was also detected in luminescence experiments under the same high-pressure conditions, wherein redshifts of the emission bands with increasing pressure were observed due to shortening of the Cu–Cu distances. Additionally, ab initio studies were carried out which confirmed the results obtained experimentally, although unfortunately, the phase transition was not predicted.

Direct Observation of the Pressure-Induced Structural Variation in Gold Nanoclusters and the Correlated Optical Response.

The ability to gradually modify the atomic structures of nanomaterials and directly identify such structural variation is important in nanoscience research. Here, we present the first example of a high-pressure single-crystal X-ray diffraction analysis of atomically precise metal nanoclusters. The pressure-dependent, subangstrom structural evolution of an ultrasmall gold nanoparticle, Au25S18, has been directly identified. We found that a 0.1 Å decrease of the Au-Au bond length could induce a blue-shift of 30 nm in the photoluminescence spectra of gold nanoclusters. From theoretical calculations, the origins of the blue-shift and enhanced photoluminescence under pressure are investigated, which are ascribed to molecular orbital symmetry and conformational locking, respectively. The combination of the high-pressure in situ X-ray results with both theoretical and experimental optical spectra provides a direct and generalizable avenue to unveil the underlying structure-property relations for nanoclusters and nanoparticles which cannot be obtained through traditional physical chemistry measurements.

Tracking structural phase transitions via single crystal x-ray diffraction at extreme conditions: advantages of extremely brilliant source

Highly brilliant synchrotron source is indispensable to track pressure-induced phenomena in confined crystalline samples in megabar range. In this article, a number of experimental variables affecting the quality high-pressure single-crystal x-ray diffraction data is discussed. An overview of the recent advancements in x-ray diffraction techniques at extreme conditions, in the frame of European Synchrotron Radiation Facility (ESRF)- Extremely Bright Source (EBS), is presented. Particularly, ID15b and ID27 beamlines have profited from the source upgrade, allowing for measurements of a few-micron crystals in megabar range. In case of ID27, a whole new beamline has been devised, including installation of double-multilayer mirrors and double crystal monochromator and construction of custom-made experimental stations. Two case studies from ID27 and ID15b are presented. Hypervalent CsI3 crystals, studied up to 24 GPa, have shown a series of phase transitions: Pnma → P-3c1→ Pm-3 n. First transition leads to formation of orthogonal linear iodine chains made of I3 -. Transformation to the cubic phase at around 21.7 GPa leads to equalization of interatomic I–I distances and formation of homoleptic In m- chains. The second study investigates elastic properties and structure of jadarite, which undergoes isosymmetric phase transition around 16.6 GPa. Despite a few-micron crystal size, twinning and dramatic loss of crystal quality, associated with pressure-induced phase transitions, crystal structures of both compounds have been determined in a straightforward matter, thanks to the recent developments within ESRF-EBS.

Stabilization mechanism of molecular orbital crystals in IrTe2

Doped IrTe2 is considered a platform for topological superconductivity and therefore receives currently a lot of interest. In addition, the superconductivity in these materials exists in close vicinity to electronic order and the formation of molecular orbital crystals, which we explore here by means of high-pressure single crystal x-ray diffraction in combination with density functional theory. Our crystallographic refinements provide detailed information about the structural evolution as a function of applied pressure up to 42 GPa. Using this structural information for density functional theory calculations, we show that the local multicenter bonding in IrTe2 is driven by changes in the Ir-Te-Ir bond angle. When the electronic order sets in, this bond angle decreases drastically, leading to a stabilization of a multicenter molecular orbital bond. This unusual local mechanism of bond formation in an itinerant material provides a natural explanation for the different electronic orders in IrTe2. It further illustrates the strong coupling of the electrons with the lattice and is most likely relevant for the superconductivity in this material.

The new Ca(Fe,Al)2O4 phase with calcium ferrite-type structure, a likely carrier of Al in the transition zone and lower mantle

Synchrotron-based high-pressure single-crystal X-ray diffraction experiments were conducted on a new CaFe1.2Al0.8O4 phase at ambient temperature and up to a maximum pressure of 61 GPa. Crystals of CaFe1.2Al0.8O4 were synthesized at 24 GPa and 1500 °C. This phase has orthorhombic unit cell parameters (a = 8.9785(1) Å, b = 2.9158(1) Å, c = 10.4253(6) Å, V = 286(3) Å3, Z = 8), crystallizes with a space group Pnma, and exhibits K0,T of 195(2) GPa. At pressures ∼50 GPa, unit cell volume of CaFe1.2Al0.8O4 drops by about 7% over a small pressure interval. By combining results from synchrotron-based high-pressure single-crystal X-ray diffraction and electronic structure calculations, it is shown that these changes in the compression behaviour are associated with changes of the electronic state of iron in the octahedral site. Thus, CaFe1.2Al0.8O4 is stable under the conditions of the transition zone and lower mantle and, therefore, may be considered as a likely Al carrier in the Earth's deep geospheres.

Pressure Tuning of Coupled Structural and Spin State Transitions in the Molecular Complex [Fe(H2B(pz)2)2(phen)

The large volume change, which accompanies the molecular spin crossover (SCO) phenomenon in some transition metal complexes, prompts frequently the coupling of the SCO with other instabilities. Understanding the driving mechanism(s) of such coupled phase transitions is not only important for fundamental reasons but also provides scope for the development of multifunctional materials. The general theoretical expectation is that the coupling has elastic origin, and the sequence of transitions can be tuned by an externally applied pressure, but dedicated experiments remain scarce. Here, we used high-pressure and low-temperature single-crystal X-ray diffraction to investigate the high-spin (HS) to low-spin (LS) transitions in the molecular complexes [FeII(H2B(pz)2)2(bipy)] and [FeII(H2B(pz)2)2(phen)]. In the bipyridine complex, the SCO is continuous and isostructural over the whole T, P-range (100-300 K, 0-2 GPa). In the phenanthroline derivative, however, the SCO is concomitant with a symmetry-breaking transition (C2/c to P1̅). Structural analysis reveals that the coupling between the two phenomena can be tuned by external pressure from a virtually simultaneous HSC2/c-LSP1̅ transition to the sequence of HSC2/c-LSC2/c-LSP1̅ transitions. The correlation of spontaneous strain and order parameter behaviors highlights that the "separated" transitions remain still connected via strain coupling, whereas the "simultaneous" transitions are partially split.

Correlating chemical bonds with glass formation in coordination polymers: a combined X-ray electron density and high-pressure single-crystal X-ray diffraction study

Correlating chemical bonds with glass formation in coordination polymers: a combined X-ray electron density and high-pressure single-crystal X-ray diffraction study

Pressure-Driven Phase Transition in Two-Dimensional Perovskite MHy2PbBr4

The application of high pressure allows tuning physicochemical properties of materials by changing interatomic distances. Pressure may also induce structural phase transitions into new phases with enhanced or novel functional properties. Here, we report complementary high-pressure single-crystal X-ray diffraction, Raman spectroscopy, and optical studies of a two-dimensional (2D) perovskite, MHy2PbBr4, comprising a very small spacer cation (methylhydrazinium, MHy+). This crystal exhibits highly desired ferroelectric and extraordinary multiple linear and nonlinear optical (NLO) properties. Single-crystal X-ray diffraction shows that MHy2PbBr4 undergoes an unusual Pmn21 → P21 phase transition near 4 GPa, associated with the extrusion of some MHy+ cations from the interlayer space into voids located within the inorganic sheets, not reported for any 2D hybrid perovskite. The transport of counter cations leads to a significant increase of Pb–NH2 interactions, an unprecedented threefold increase of positive linear compressibility perpendicular to the polyanionic layers and a large negative linear compressibility of −22.39 TPa–1 within the layers. The Raman data confirm the association of the phase transition with strong distortion of the crystal structure and reorganization of the hydrogen bond network, while the absorption spectra of the compressed ambient-pressure Pmn21 phase show the band gap narrowing, followed by its widening in the high-pressure P21 phase. A similar change in the pressure dependence from a red shift to a blue shift is also observed for the free-exciton (FE) photoluminescence (PL). Furthermore, the pressure-induced phase transition leads to a giant enhancement of PL intensity, especially pronounced for the broad-band emission attributed to the self-trapped excitons (STEx). We attribute the effects, observed in absorption and PL spectra, to the shortening of Pb–Br bonds in the ambient pressure phase and increased distortion of the inorganic layers and tilts of PbBr6 octahedra in the high-pressure phase. Overall, our results for a 2D hybrid compound comprising very small spacer cations extend the understanding of the pressure effect on the properties of 2D hybrid perovskites in general and demonstrate a very different behavior under compression compared to the analogues with large organic cations. They revealed that the structure–strain mechanism can be used for engineering new high-pressure phases with unusual structural, mechanical, and optoelectronic properties.

Pressure-induced metallization in the absence of a structural transition in the layered ferromagnetic insulator Cr2Ge2Te6

We report the crystallographic and electrical transport properties of single crystals of the ferromagnetic two-dimensional (2D) material ${\mathrm{Cr}}_{2}{\mathrm{Ge}}_{2}{\mathrm{Te}}_{6}$ under high pressure. In contrast to previous studies, our high-pressure single-crystal x-ray diffraction under hydrostatic conditions shows prominent anisotropic compressibility in the layered structure of the crystalline $R\overline{3}$ phase of ${\mathrm{Cr}}_{2}{\mathrm{Ge}}_{2}{\mathrm{Te}}_{6}$ without any structural phase transitions up to 20 GPa. Our data confirm a distinct and irreversible crystalline-amorphous transformation in ${\mathrm{Cr}}_{2}{\mathrm{Ge}}_{2}{\mathrm{Te}}_{6}$. The loss of crystallinity starts at 20 GPa; however, the crystalline phase and amorphous state coexist even at the maximum pressure of 31.2 GPa. High-pressure powder x-ray diffraction data and electrical resistivity measurements of ${\mathrm{Cr}}_{2}{\mathrm{Ge}}_{2}{\mathrm{Te}}_{6}$ using NaCl as the pressure-transmitting medium reveal an insulator-to-metal transition in the absence of a phase transition at \ensuremath{\sim}3.9 GPa; at a considerably lower pressure than the previously reported (7--14 GPa). Density functional theory calculations demonstrate the density of states around the Fermi level are primarily dominated by Cr $3d$ and Te $5p$ states. Hence the large reduction of Cr-Te bond lengths within the ${\mathrm{CrTe}}_{6}$ octahedra under compression is most likely responsible for the band-gap closure. This study clarifies that the phase stability and onset of metallization pressure in the ${\mathrm{Cr}}_{2}{\mathrm{Ge}}_{2}{\mathrm{Te}}_{6}$ sample are sensitive to the hydrostatic environments and demonstrates how pressure can be used to tune the physical properties of 2D ferromagnetic compounds.

Crystal structure solution of a high-pressure polymorph of scintillating MgMoO4 and its electronic structure

The structure of the potentially scintillating high-pressure phase of $\ensuremath{\beta}\text{\ensuremath{-}}{\mathrm{MgMoO}}_{4}$ ($\ensuremath{\gamma}\text{\ensuremath{-}}{\mathrm{MgMoO}}_{4}$) has been solved by means of high-pressure single-crystal x-ray diffraction. The phase transition occurs above 1.5 GPa and involves an increase of the Mo coordination from fourfold to sixfold accommodated by a rotation of the polyhedra and a concommitant bond stretching resulting in an enlargement of the $c$ axis. A previous high-pressure Raman study had proposed such changes with a symmetry change to space group $P2/c$. Here it has been found that the phase transition is isosymmetrical ($C2/m\phantom{\rule{4pt}{0ex}}\ensuremath{\longrightarrow}\phantom{\rule{4pt}{0ex}}C2/m$). The bulk moduli and the compressibilities of the crystal axes of both the low- and the high-pressure phase, have been obtained from equation of state fits to the pressure evolution of the unit-cell parameters which were obtained from powder x-ray diffraction up to 12 GPa. The compaction of the crystal structure at the phase transition involves a doubling of the bulk modulus ${B}_{0}$ changing from 60.3(1) to 123.7(8) GPa and a change of the most compressible crystal axis from the (0, $b$, 0) direction in $\ensuremath{\beta}\text{\ensuremath{-}}{\mathrm{MgMoO}}_{4}$ to the ($0.9a$, 0, $0.5a$) direction in $\ensuremath{\gamma}\text{\ensuremath{-}}{\mathrm{MgMoO}}_{4}$. The lattice dynamical calculations performed here on $\ensuremath{\gamma}\text{\ensuremath{-}}{\mathrm{MgMoO}}_{4}$ served to explain the Raman spectra observed for the high-pressure phase of $\ensuremath{\beta}\text{\ensuremath{-}}{\mathrm{MgMoO}}_{4}$ in a previous work demonstrating that the use of internal modes arguments in which the ${\mathrm{MoO}}_{n}$ polyhedra are considered as separate vibrational units fails at least in this molybdate. The electronic structure of $\ensuremath{\gamma}\text{\ensuremath{-}}{\mathrm{MgMoO}}_{4}$ was also calculated and compared with the electronic structures of $\ensuremath{\beta}\text{\ensuremath{-}}{\mathrm{MgMoO}}_{4}$ and ${\mathrm{MgWO}}_{4}$ shedding some light on why ${\mathrm{MgWO}}_{4}$ is a much better scintillator than any of the phases of ${\mathrm{MgMoO}}_{4}$. These calculations yielded for $\ensuremath{\gamma}\text{\ensuremath{-}}{\mathrm{MgMoO}}_{4}$ a ${Y}_{2}\mathrm{\ensuremath{\Gamma}}\ensuremath{\longrightarrow}\mathrm{\ensuremath{\Gamma}}$ indirect band gap of 3.01 eV in contrast to the direct bandgaps of $\ensuremath{\beta}\text{\ensuremath{-}}{\mathrm{MgMoO}}_{4}$ (3.58 eV at $\mathrm{\ensuremath{\Gamma}}$) and ${\mathrm{MgWO}}_{4}$ (3.32 eV at $Z$).