41 research outputs found
Pressure dependent electronic properties of MgO polymorphs: A first-principles study of Compton profiles and autocorrelation functions
The first-principles periodic linear combination of atomic orbitals method
within the framework of density functional theory implemented in the CRYSTAL06
code has been applied to explore effect of pressure on the Compton profiles and
autocorrelation functions of MgO. Calculations are performed for the B1, B2,
B3, B4, B8_1 and h-MgO polymorphs of MgO to compute lattice constants and bulk
moduli. The isothermal enthalpy calculations predict that B4 to B8_1, h-MgO to
B8_1, B3 to B2, B4 to B2 and h-MgO to B2 transitions take place at 2, 9, 37, 42
and 64 GPa respectively. The high pressure transitions B8_1 to B2 and B1 to B2
are found to occur at 340 and 410 GPa respectively. The pressure dependent
changes are observed largely in the valence electrons Compton profiles whereas
core profiles are almost independent of the pressure in all MgO polymorphs.
Increase in pressure results in broadening of the valence Compton profiles. The
principal maxima in the second derivative of Compton profiles shifts towards
high momentum side in all structures. Reorganization of momentum density in the
B1 to B2 structural phase transition is seen in the first and second
derivatives before and after the transition pressure. Features of the
autocorrelation functions shift towards lower r side with increment in
pressure.Comment: 19 pages, 8 figures, accepted for publication in Journal of Materials
Scienc
Experimental and theoretical confirmation of an orthorhombic phase transition in niobium at high pressure and temperature
Compared to other body-centered cubic (bcc) transition metals, Nb has been the subject of fewer compression studies and there are still aspects of its phase diagram which are unclear. Here, we report a combined theoretical and experimental study of Nb under high pressure and temperature. We present the results of static laser-heated diamond anvil cell experiments up to 120 GPa using synchrotron-based fast x-ray diffraction combined with ab initio quantum molecular dynamics simulations. The melting curve of Nb is determined and evidence for a solid-solid phase transformation in Nb with increasing temperature is found. The high-temperature phase of Nb is orthorhombic Pnma. The bcc-Pnma transition is clearly seen in the experimental data on the Nb principal Hugoniot. The bcc-Pnma coexistence observed in our experiments is explained. Agreement between the measured and calculated melting curves is very good except at 40â60 GPa where three experimental points lie below the theoretical melting curve by 250 K (or 7%); a possible explanation is given
Understanding high pressure hydrogen with a hierarchical machine-learned potential
The hydrogen phase diagram has a number of unusual features which are
generally well reproduced by density functional calculations. Unfortunately,
these calculations fail to provide good physical insights into why those
features occur. In this paper, we parameterize a model potential for molecular
hydrogen which permits long and large simulations. The model shows excellent
reproduction of the phase diagram, including the broken-symmetry Phase II, an
efficiently-packed phase III and the maximum in the melt curve. It also gives
an excellent reproduction of the vibrational frequencies, including the maximum
in the vibrational frequency and negative thermal expansion. By
detailed study of lengthy molecular dynamics, we give intuitive explanations
for observed and calculated properties. All solid structures approximate to
hexagonal close packed, with symmetry broken by molecular orientation. At high
pressure, Phase I shows significant short-ranged correlations between molecular
orientations. The turnover in Raman frequency is due to increased coupling
between neighboring molecules, rather than weakening of the bond. The liquid is
denser than the close-packed solid because, at molecular separations below
2.3\AA, the favoured relative orientation switches from
quadrupole-energy-minimising to steric-repulsion-minimising. The latter allows
molecules to get closer together, without atoms getting closer but this cannot
be achieved within the constraints of a close-packed layer
Thermostatic properties of nitrate molten salts and their solar and eutectic mixtures
Nitrate molten salts are extensively used for sensible heat storage in Concentrated Solar Power (CSP)
plants and thermal energy storage (TES) systems. They are the most promising materials for latent heat
storage applications. By combining classical molecular dynamics and differential scanning calorimetry
experiments, we present a systematic study of all thermostatic, high temperature properties of pure
KNO3 and NaNO3 salts and their eutectic and âsolar saltâ mixtures, technologically relevant. We first
study, in solid and liquid regimes, their mass densities, enthalpies, thermal expansion coefficients and
isothermal compressibilities. We then analyze the cP and cV specific heats of the pure salts and of
the liquid phase of the mixtures. Our theoretical results allow to resolve a long-standing experimental
uncertainty about the cP(T) thermal behaviour of these systems. In particular, they revisit empirical laws
on the cP(T) behaviour, extensively used at industrial level in the design of TES components employing
the âsolar saltâ as main storage material. Our findings, numerically precise and internally consistent, can
be used as a reference for the development of innovative nanomaterials based on nitrate molten salts,
crucial in technologies as CSP, waste heat recovery, and advanced adiabatic compressed air energy
storage
Stabilization of body-centred cubic iron under inner-core conditions
The Earths solid core is mostly composed of iron. However, despite being central to our understanding of core properties, the stable phase of iron under inner-core conditions remains uncertain. The two leading candidates are hexagonal close-packed and body-centred cubic (bcc) crystal structures, but the dynamic and thermodynamic stability of bcc iron under inner-core conditions has been challenged. Here we demonstrate the stability of the bcc phase of iron under conditions consistent with the centre of the core using ab initio molecular dynamics simulations. We find that the bcc phase is stabilized at high temperatures by a diffusion mechanism that arises due to the dynamical instability of the phase at lower temperatures. On the basis of our simulations, we reinterpret experimental data as support for the stability of bcc iron under inner-core conditions. We suggest that the diffusion of iron atoms in solid state may explain both the anisotropy and the low shear modulus of the inner core.Funding Agencies|Swedish Research Council (VR) [2013-5767, 2014-4750]; National Magnetic Confinement Fusion Program of China [2015GB118000]; China Scholarship Council; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]</p
Simulation of shock-induced melting of Ni using molecular dynamics coupled to a two-temperature model
Using nonequilibrium molecular dynamics (MD) simulations we study shock-induced melting in Ni with an embedded atom method (EAM). Dynamic melting is probed by the pair correlation function, and we find a melting lattice temperature of Tmelt =6400±300 K for a melting pressure of Pmelt =275±10 GPa. When a combined MD+TTM (two-temperature model) approach is used to include electronic heat conduction and electron-phonon coupling, Pmelt and Tmelt change. For a given pressure, the temperature behind the shock decreases due to electronic heat diffusion into the cold, unshocked material. This cooling of the material behind the shock slightly increases the melting pressure compared to simulations without electronic heat conduction and electron-phonon coupling. The decrease in the temperature behind the shock front is enhanced if the electron-phonon coupling is artificially made larger. We also explore the feasibility of using x-ray diffraction to detect melting. © 2006 The American Physical Society