MnWO4 has attracted attention because of its ferroelectric property induced by frustrated helical spin order. Strong spin-lattice interaction is necessary to explain ferroelectricity associated with this type of magnetic order.We have conducted thermal expansion measurements along the a, b, c axes revealing the existence of strong anisotropic lattice anomalies at T1=7.8 K, the temperature of the magnetic lock-in transition into a commensurate low-temperature (reentrant paraelectric) phase. The effect of hydrostatic pressure up to 1.8 GPa on the FE phase is investigated by measuring the dielectric constant and the FE polarization. The low- temperature commensurate and paraelectric phase is stabilized and the stability range of the ferroelectric phase is diminished under pressure.
Results of a series of molecular dynamics simulations of cubic siliceous zeolites suggest that pressure-induced softening -- the phenomenon in which a material becomes progressively more compressible under pressure -- is likely to be a common feature of framework materials that show negative thermal expansion. The correlation between the negative thermal expansion and the pressure-induced softening is investigated on the basis of thermodynamics.
The effect of pressure on the thermal expansion of solid CH$_4$ is calculated for the low temperature region where the contributions from phonons and librons can be neglected and only the rotational tunnelling modes are essential. The effect of pressure is shown to increase the magnitude of the peaks of the negative thermal expansion and shifts the positions of the peaks to the low-temperature region, which goes asymptotically to zero temperature with increasing pressure. The Gruneisen thermodynamical parameter for the rotational tunnelling modes is calculated. It is large, negative, and incre…
Thermal conductivity of the most abundant element in the planetary core, Iron (Fe) is measured up to Earth's outer core pressure $\sim 120$ GPa. The measurements are carried out using the laser heated diamond anvil cell facility, where the absorbed power by Fe metal foil is calculated using thermodynamical equation. The thermal conductivity of $γ-Fe$ linearly increases up to a maximum experimental pressure 40 GPa. Thermal conductivity of $ε-Fe$ measured by us shows a saturated value $\sim$ 52 ($\pm$ 5) $Wm^{-1}K^{-1}$ in the pressure range 77 - 120 GPa. At different pressures temperature depen…
Pressure and temperature dependence of the negative thermal expansion in Zn(CN)$_2$ is fully investigated using molecular dynamics simulations with a built potential model. The advantage of this study allows us to reproduce all the exotic behaviours of the material, including the negative thermal expansion (NTE), the reduction of NTE with elevated temperature, the pressure enhancement of NTE and the pressure-induced softening. Results of the study provide us detailed data to link the properties in the energy space and the real space, giving us insights to understand the properties and the conn…
The thermal conductivity of boron arsenide (BAs) is believed to be influenced by phonon scattering selection rules due to its special phonon dispersion. Compression of BAs leads to significant changes in phonon dispersion, which allows for a test of first principles theories for how phonon dispersion affects three- and four-phonon scattering rates. This study reports the thermal conductivity of BAs from 0 to 30 GPa. Thermal conductivity vs. pressure of BAs is measured by time-domain thermoreflectance with a diamond anvil cell. In stark contrast to what is typical for nonmetallic crystals, BAs …
We report high pressure X-ray diffraction and a detailed systematic Raman measurements on $ReS_2$ sample, which is mechanically exfoliated from a single crystal. A few new Bragg peaks are observed to emerge above 6 GPa indicating a structural transition from distorted $1T$ to distorted $1T$$^{\prime}$ in triclinic structure. The same is corroborated by appearance of new Raman modes in the same pressure range. Softening of the Raman modes corresponding to $Re$ atom vibrations are observed in the distorted $1T$$^{\prime}$ phase in the pressure range 15-25 GPa. In the same pressure range the anom…
The long standing controversy between the melting curves of the bcc Mo,Ta,W and vanadium (V) metals measured by diamond anvil Cells (DAC) and the shock dynamic experiments is explained by the behavior the liquid or solid pressure transmitting mediums compressed by the thermal expansion of the these transition metals. This explains the observed isobaric behavior of the laser heated DAC experiments containing different transmitting mediums reported in the literature, thus solving the standing enigma described in very many publications.
We report on the determination of high-pressure elasticity from thermal diffuse x-ray scattering of magnesium oxide at pressures up to 28 GPa. We find that the full elasticity tensor as a function of pressure can be extracted from x-ray scattering of single crystals. This enables the simultaneous measurement of elasticity and crystal structure from a single experiment and thus marks a decisive step towards establishing reliable calibration for extreme pressures. Elastic constants can be extracted with this method from small crystals of arbitrary symmetry, shape and optical properties and will …
We study the thermal transport properties of three CaF$_{2}$ polymorphs up to a pressure of 30 GPa using first-principle calculations and an interatomic potential based on machine learning. The lattice thermal conductivity $κ$ is computed by iteratively solving the linearized Boltzmann transport equation (BTE) and by taking into account three-phonon scattering. Overall, $κ$ increases nearly linearly with pressure, and we show that the recently discovered $δ$-phase with $P\bar{6}2m$ symmetry and the previously known $γ$-CaF$_{2}$ high-pressure phase have significantly lower lattice thermal cond…
Negative thermal expansion materials are important and desirable in science and engineering applications. However, natural materials with isotropic negative thermal expansion are rare and usually unsatisfied in performance. Here, we propose a novel method to achieve negative thermal expansion via a metamaterial approach. The metamaterial is constructed with unit cells that combine bi-material strips and anti-chiral structures. Both experimental and simulation results display isotropic negative thermal expansion properties. The coefficient of negative thermal expansion of the metamaterials is d…
Controlling the thermal expansion of materials is of great technological importance. Uncontrolled thermal expansion can lead to failure or irreversible destruction of structures and devices. In ordinary crystals, thermal expansion is governed by the asymmetry of the microscopic binding potential, which cannot be adjusted easily. In artificial crystals called metamaterials, thermal expansion can be controlled by structure. Here, following previous theoretical work, we fabricate three-dimensional two-component polymer microlattices by using gray-tone laser lithography. We perform cross-correlati…
Understanding various macroscopic pressure-volume-temperature properties of materials on the atomistic level has always been an ambition for physicists and material scientists. Particularly, some materials such as zirconium tungstate (ZrW2O8), exhibit multiple exotic properties including negative thermal expansion (NTE) and pressure-induced amorphization (PIA). Here, using machine-learning based deep potential, we trace both of the phenomena in ZrW2O8 back to a common atomistic origin, where the nonbridging O atoms play a critical role. We demonstrate that the nonbridging O atoms confer great …
We investigate the equation of state and elastic properties of hcp iron at high pressures and high temperatures using first principles linear response linear-muffin-tin-orbital method in the generalized-gradient approximation. We calculate the Helmholtz free energy as a function of volume, temperature, and volume-conserving strains, including the electronic excitation contributions from band structures and lattice vibrational contributions from quasi-harmonic lattice dynamics. We perform detailed investigations on the behavior of elastic moduli and equation of state properties as functions of …
Thermal expansion in materials can be accurately modeled with careful anharmonic phonon calculations within density functional theory. However, because of interest in controlling thermal expansion and the time consumed evaluating thermal expansion properties of candidate materials, either theoretically or experimentally, an approach to rapidly identifying materials with desirable thermal expansion properties would be of great utility. When the ionic bonding is important in a material, we show that the fraction of crystal volume occupied by ions, (based upon ionic radii), the mean bond coordina…
Thermal expansion is a problem in many technological applications and its control represents a challenge in materials design. In this Letter, after studying the correlation between thermal expansion, cubic-to-rhombohedral transition and lattice parameter of ReO3-type structures, I show how in the different methods for controlling thermal expansion the key element is actually the lattice parameter. By varying the lattice parameter through external pressure, chemical modifications or other methods, the single-well potential energy of the octahedral rotation, responsible for Negative Thermal Expa…
We elaborate a modification of the deformable two-sublattice Mitsui model of [Levitskii R.R. et al., Phys. Rev. B. 2003, 67, 174112] and [Levitskii R.R. et al., Condens. Matter Phys., 2005, 8, 881] that consistently takes into account diagonal components of the strain tensor, arising either due to external pressures or due to thermal expansion. We calculate the related to those strains thermal, piezoelectric, and elastic characteristics of the system. Using the developed fitting procedure, a set of the model parameters is found for the case of Rochelle salt crystals, providing a satisfactory a…
The thermal expansion at constant pressure of solid CD$_4$ III is calculated for the low temperature region where only the rotational tunneling modes are essential and the effect of phonons and librons can be neglected. It is found that in mK region there is a giant peak of the negative thermal expansion. The height of this peak is comparable or even exceeds the thermal expansion of solid N$_2$, CO, O$_2$ or CH$_4$ in their triple points. It is shown that like in the case of light methane, the effect of pressure is quite unusual: as evidenced from the pressure dependence of the thermodynamic G…
The thermal expansion of the wide band gap semiconductor MgSiN$_{2}$ has been determined using density functional calculations in combination with the quasi-harmonic approximation. We find that the thermal expansion is rather small in good agreement with previous experimental studies. However, the present calculations suggest that the thermal expansion of the system is more isotropic. Additional thermodynamic properties such as the Gr{ü}neisen parameter and the heat capacity at constant pressure have also been determined and found to be in good agreement with available experiments.
The thermal expansion of pure and Ti-bearing fused silica was estimated using free energy minimization lattice dynamics calculations in the quasiharmonic approximation. While the calculations give the expected drop in the coefficient of thermal expansion in going from quartz to fused silica, the overall shape of the coefficient of thermal expansion versus temperature curve for the high-purity and titanium-bearing fused silica is not reproduced by the quasiharmonic approximation. This result is robust and insensitive to system size and annealing density of the glass.
Thermal expansion of MAX phases along different directions tended to be different because of the anisotropy of hexagonal crystals. Herein, a new Hf2SeC phase was synthesized and confirmed to be relatively isotropic, whose coefficients of thermal expansion (CTEs) were determined to be 9.73 μK-1 and 10.18 μK-1 along a and c directions. The strong M-S bond endowed Hf2SC and Zr2SC lower CTEs than Hf2SeC and Zr2SeC. A good relationship between the thermal expansion anisotropy and the ratio of elastic stiffness constant c11 and c33 was established. This straightforward approximation could be used to…
The orthovanadates are useful as host matrices for immobilization of radioactive wastes. The thermodynamic stability of these materials is crucial for their applications in high pressure and temperatures environment. It is necessary to investigate the phonons in the entire Brillouin zone, beyond the zone-centre phonons accessible in previous Raman and infrared experiments. We have carried out extensive neutron inelastic scattering experiments to derive the phonon dispersion relation of YVO4 up to high energy transfer of 65 meV using a single crystal, which are perhaps reported for the first ti…
A simulation study of negative thermal expansion in Y2W3O12 was carried out using calculations of phonon dispersion curves through the application of density functional perturbation theory. The mode eigenvectors were mapped onto flexibility models and results compared with calculations of the mode Gruneisen parameters. It was found that many lower-frequency phonons contribute to negative thermal expansion in Y2W3O12, all of which can be described in terms of rotations of effectively rigid WO4 tetrahedra and Y-O rods. The results are strikingly different from previous phonon studies of higher-s…
A One-Dimensional Reduction Method for Calculating Thermal Expansion in Solids: Application to Orthorhombic Systems
Baikov Institute of Metallurgy and Materials Science of the Russian Academy of Sciences（俄罗斯科学院拜科夫冶金与材料科学研究所）；D. Mendeleev University of Chemical Technology of Russia, Moscow, Russia（俄罗斯国立化学技术门捷列夫大学）；HSE University, 101000 Moscow, Russia（高等经济学院）
By means of first-principles calculations, we investigate the thermal properties of silica as it evolves, under hydrostatic compression, from a stishovite phase into a CaCl$_2$-type structure. We compute the thermal conductivity tensor by solving the linearized Boltzmann transport equation iteratively in a wide temperature range, using for this the pressure-dependent harmonic and anharmonic interatomic couplings obtained from first principles. Most remarkably, we find that, at low temperatures, SiO$_2$ displays a large peak in the in-plane thermal conductivity and a highly anisotropic behavior…
We report on electronic-structure calculations for the pentacene and rubrene crystals, based on experimental crystal geometries measured at different temperatures. The results are in very good agreement with angle-resolved photoelectron spectroscopy data that indicate that the widths of the valence and conduction bands in both materials become narrower at higher temperatures. Our findings strongly suggest that the thermal bandwidth narrowing in the pentacene and rubrene crystals is primarily caused by the thermal expansion of the lattice rather than by a renormalization of the transfer integra…
Van der Waals heterostructures such as graphene/MoS$_2$ are promising candidates for plenty of optical or electronic applications, owing to advanced properties inherited from the constitutional atomic layers. Thermal expansion is an important phenomenon to be considered for the thermal stability of the van der Waals heterstructure as temperature commonly rises during the operation of nano devices. In the present work, the thermal expansion coefficient for the graphene/MoS$_2$ heterostructure is investigated by molecular dynamics simulations, and the effect from the unavoidable misfit strain on…
We use reverse non-equilibrium molecular dynamics (RNEMD) simulations to determine the thermal conductivity in $α$-RDX in the <100>, <010>, and <001> crystallographic directions. Simulations are carried out with the Smith-Bharadwaj non-reactive empirical interatomic potential [Smith & Bharadwaj, J. Phys. Chem. B 103, 3570(1999)], which represents the thermo-elastic properties of RDX with good accuracy. As an illustration, we report the temperature and pressure dependence of lattice constants of $α$-RDX, which compare well with experimental and ab initio results, as do linear and volume thermal…
The lattice parameters of two boron subnitrides, B13N2 and B50N2, have been measured as a function of temperature between 298 and 1273 K, and the corresponding thermal expansion coefficients have been determined. Thermal expansion of both boron subnitrides was found to be quasi-linear, and the volume thermal expansion coefficients of B50N2 (15.7(2) 10-6 K-1) and B13N2 (21.3(2) 10-6 K-1) are of the same order of magnitude as those of boron-rich compounds with structure related to α-rhombohedral boron. For both boron subnitrides no temperature-induced phase transitions have been observed in the …
We have used ab-initio density functional theory technique to understand the phase transitions and structural changes in various high temperature/pressure phases of LiAlO2. The electronic band structure as well as phonon spectra are calculated for various phases as a function of pressure. The phonon entropy used for the calculations of Gibbs free energy is found to play an important role in the phase stability and phase transitions among various phases. A sudden increase in the polyhedral bond lengths (Li/Al-O) signifies the change from the tetrahedral to octahedral geometry at high-pressure p…
We have investigated temperature dependence of the lattice parameters and the unit cell volume of ZnF$_2$ by neutron diffraction and have discovered negative thermal expansion (NTE) at low temperature. To understand why this simple compound exhibits NTE we performed first principle calculations. These calculations reproduce qualitatively the experimental temperature dependence of volume.
The hydration and ammonization of ZrW2O8 is known to lead to positive and negative thermal expansion behaviour respectively. We report ab-initio calculations to understand this anomalous behaviour. We identify the crucial low energy phonon modes involving translations, rotations and distortions of WO4 and ZrO6 polyhedra, which lead to NTE in ZrW2O8 in pure and ammoniated forms; however, the rotation and distortion motions get inhibited on hydration and lead to positive thermal expansion. We demonstrate that the thermal expansion coefficient could be tailored by engineering the phonon dynamics …
We have investigated the effect of ambient gas pressure (Argon) used during thermal exfoliation of graphite oxide on the number of graphene sheets in the resulting graphene. The ambience gas Ar pressures used are 80, 25, 1 atmosphere and 10-3 as well as 10-5 torr. We have found curious result that the number of graphene sheets in exfoliated graphene stack is dependent on the applied pressure for exfoliation of graphite oxide (GO). By lowering the exfoliation pressure, the numbers of sheets get reduced. The numbers of sheets in exfoliated graphene stack have been determined by Lorentzian fit of…
Thermal expansion of α-rhombohedral boron (α-B12) and two isostructural boron-rich pnictides (B12P2 and B12As2) has been studied between 298 and 1280 K by high-temperature synchrotron X-ray diffraction. For all studied phases no temperature-induced phase transitions have been observed. The observed temperature dependencies of the lattice parameters and unit cell volumes were found to be quasi-linear. Variation of the thermal expansion coefficients in the group of boron-rich pnictides (B13N2 - B12P2 - B12As2) was analyzed.
The Mu-phase, which is an intermetallic compound, can form in steels and superalloys, and significantly degrade their mechanical properties. The thermal expansion of Co7Mo6 Mu-phase have been investigated by first-principles based quasi-harmonic Debye-Grüneisen approximation and by comparing the free energies calculated along different paths of thermal expansion. The calculations were carried out for temperatures from 0 K to 1500 K which below the decomposition temperature of Co7Mo6. The electronic, vibrational and magnetic energy contributions to the free energy were accounted. The thermal ex…
We report measurement of temperature dependence of phonon spectra in quasi one-dimensional metal cyanides MCN (M=Cu, Ag and Au). Ab initio lattice dynamics calculations have been performed to interpret the phonon-spectra as well as to understand the anamolous thermal expansion behavior in these compounds. We bring out the differences in the phonon mode behavior to explain the differences in the thermal expansion behavior among the three compounds. The chain-sliding modes are found to contribute maximum to the negative thermal expansion along c axis in the Cu and Ag compounds, while the same mo…
We investigate detailed lattice dynamics of copper halides CuX (X=Cl, Br, I) using neutron inelastic scattering measurements and ab-initio calculations aimed at a comparative study of their thermal expansion behavior. We identify the low energy phonons which soften with pressure and are responsible for negative thermal expansion. The eigenvector analysis of these modes suggests that softening of the transverse-acoustic modes would lead to NTE in these compounds. The calculations are in very good agreement with our measurements of phonon spectra and thermal expansion behavior as reported in the…
Some anisotropy in both mechanical and thermodynamical properties of bismuth is expected. A combination of density functional theory total energy calculations and density functional perturbation theory in the local density approximation is used to compute the elastic constants at 0 K using a finite strain approach and the thermal expansion tensor in the quasiharmonic approximation. The overall agreement with experiment is good. Furthermore, the anisotropy in the thermal expansion is found to arise from the anisotropy in both the directional compressibilities and the directional Grüneisen funct…
We have investigated the anisotropic thermal expansion of graphite using ab-initio calculation of lattice dynamics and anharmonicity of the phonons, which reveal that the negative thermal expansion (NTE) in the a-b plane below 600 K and very large positive thermal expansion along the c-axis up to high temperatures arise due to various phonons polarized along the c-axis. While the NTE arises from the anharmonicity of transverse phonons over a broad energy range up to 60 meV, the large positive expansion along the c-axis occurs largely due to the longitudinal optic phonon modes around 16 meV and…
Recent measurements of an unusual high thermal conductivity of around 1000 W m-1 K-1 at room temperature in cubic boron arsenide (BAs) confirm predictions from theory and suggest potential applications of this semiconductor compound for thermal management applications. Knowledge of the thermal expansion coefficient and Grüneisen parameter of a material contributes both to the fundamental understanding of its lattice anharmonicity and to assessing its utility as a thermal-management material. However, previous theoretical calculations of the thermal expansion coefficient and Grüneisen parameter…
Given the unique optical properties of LiF, it is often used as an observation window in high-temperature and pressure experiments; and, hence, estimates of its transmission properties are necessary to interpret observations. Since direct measurements of the thermal conductivity of LiF at the appropriate conditions are difficult, we resort to molecular simulation methods. Using the Belonoshko et al. (2000) empirical potential validated against ab initio phonon density of states, we estimate the thermal conductivity of LiF at high temperatures (1000-4000K) and pressures (100-400 GPa) with the G…
A definition of the Grüneisen parameters for anisotropic materials is derived based on the response of phonon frequencies to uniaxial stress perturbations. This Grüneisen model relates the thermal expansion in a given direction ($α_{ii}$) to one element of the elastic compliance tensor, which corresponds to the Young's modulus in that direction ($Y_{ii}$). The model is tested through ab initio prediction of thermal expansion in zinc, graphite, and calcite using density functional perturbation theory, indicating that it could lead to increased accuracy for structurally complex systems. The dire…
We present temperature dependent inelastic neutron scattering measurments, accompanied byab-initio calculations of phonon spectra and elastic properties as a function of pressure to understand anharmonicity of phonons and to study the mechanism of negative thermal expansion and negative linear compressibility behaviour of ZnAu2(CN)4. The mechanism is identified in terms of specific anharmonic modes that involve bending of the Zn(CN)4-Au- Zn(CN)4 linkage. The high-pressure phase transition at about 2 GPa is also investigated and found to be related to softening of a phonon mode at the L-point a…
The thermal expansion behavior of metal fluorides can be tuned by choosing appropriate metal cation. We present ab-initio lattice dynamical studies on the metal fluorides (CaZrF6, MgZrF6 and SrZrF6) and identify the anharmonic phonon modes responsible for the negative thermal expansion in these materials. These phonons involve ZrF6 polyhedral rotational motion, which leads to large transverse amplitude of the vibrations of the fluorine atom in the Zr-F-Zr bond. The compounds with larger anisotropy in the thermal amplitude of the fluorine atoms show larger NTE behaviour. This has enabled to und…
Based on first-principles calculation using density functional theory, we study the vibrational properties and thermal expansion of mono-atomic two-dimensional honeycomb lattices: graphene, silicene, germanene and blue phosphorene. We focus on the similarities and differences of their properties, and try to understand them from their lattice structures. We illustrate that, from graphene to blue phosphorene, phonon bandgap develops due to large buckling-induced mixing of the in-plane and out-of-plane phonon modes. This mixing also influences their thermal properties. Using quasi-harmonic approx…
Phonon transport of recently-fabricated $\mathrm{Na_2He}$ at high pressure is investigated from a combination of first-principles calculations and the linearized phonon Boltzmann equation within the single-mode relaxation time approximation (RTA). The calculated room-temperature lattice thermal conductivity is 149.19 $\mathrm{W m^{-1} K^{-1}}$, which is very close to one of Si. It is found that low-frequency optical modes comprise 16\% of the lattice thermal conductivity, while high-frequency optical modes have negligible contribution. The high lattice thermal conductivity is due to large grou…
Metal-organic frameworks often display large positive or negative thermal expansion coefficients. MOF-74, a material envisioned for many applications does not display such a behavior. For this system, temperature-dependent x-ray diffraction reveals particularly small negative thermal expansion coefficients perpendicular and positive ones parallel to the hexagonally arranged pores. The observed trends are explained by combining state-of-the-art density-functional theory calculations with the Grüneisen theory of thermal expansion, which allows tracing back thermal expansion to contributions of i…
