Ionization of highly compressed ammonia has previously been predicted by computation. Here, the authors provide experimental evidence for this autoionization process at high pressures, showing the transformation of molecular ammonia into ammonium amide.

/pdf/ammonia-as-a-case-study-for-the-spontaneous-ionization-of-a-43dukoq5c2.pdf

Ammonia as a case study for the spontaneous ionization of a simple hydrogen-bonded compound

We have developed an efficient and reliable methodology for crystal structure prediction, merging ab initio total-energy calculations and a specifically devised evolutionary algorithm. This method allows one to predict the most stable crystal structure and a number of low-energy metastable structures for a given compound at any P-T conditions without requiring any experimental input. Extremely high (nearly 100%) success rate has been observed in a few tens of tests done so far, including ionic, covalent, metallic, and molecular structures with up to 40 atoms in the unit cell. We have been able to resolve some important problems in high-pressure crystallography and report a number of new high-pressure crystal structures (stable phases: epsilon-oxygen, new phase of sulphur, new metastable phases of carbon, sulphur and nitrogen, stable and metastable phases of CaCO3). Physical reasons for the success of this methodology are discussed.

Crystal structure prediction using ab initio evolutionary techniques: principles and applications.

We have developed an efficient and reliable methodology for crystal structure prediction, merging ab initio total-energy calculations and a specifically devised evolutionary algorithm. This method allows one to predict the most stable crystal structure and a number of low-energy metastable structures for a given compound at any P-T conditions without requiring any experimental input. Extremely high success rate has been observed in a few tens of tests done so far, including ionic, covalent, metallic, and molecular structures with up to 40 atoms in the unit cell. We have been able to resolve some important problems in high-pressure crystallography and report a number of new high-pressure crystal structures. Physical reasons for the success of this methodology are discussed.

Crystal structure prediction using ab initio evolutionary techniques: principles and applications

We present a systematic and comparative study of the pressure-induced solidification of 11 frequently used pressure transmitting fluids using the ruby fluorescence technique in a diamond anvil cell. These fluids are 1 : 1 and 5 : 1 iso-n pentane, 4 : 1 deuterated methanol–ethanol, 16 : 3 : 1 deuterated methanol–ethanol-water, 1 : 1 FC84-FC87 Fluorinert, Daphne 7474, silicone oil, as well as nitrogen, neon, argon and helium. The data provide practical guidelines for the use of these fluids in high pressure experiments up to 50 GPa.

https://iopscience.iop.org/article/10.1088/0022-3727/42/7/075413/pdf

Hydrostatic limits of 11 pressure transmitting media

Premises of creation of Internet portal designed to provide access to participants of educational and scientific process for the joint creation, consolidation, concentration and rapid spreading of educational and scientific information resources in its own depository are considered. CMS-based portal content management systems’ potentiality is investigated. Architecture for Internet portal of MES of Ukraine’s information resources is offered.

Створення порталу інформаційно-довідкових ресурсів міністерства освіти і науки україни

Compression versus pressure at ambient temperature has been measured for tantalum, gold, and platinum to $94\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ and for aluminum, copper, and tungsten to $153\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$, in a diamond anvil cell. Standard synchrotron x-ray diffraction accuracy in the volume determination could be achieved to the maximum pressure. The current data set is used to recalibrate the static pressure scale based on the ruby luminescence, confirming recent suggestions of an underestimation of pressure. Using an updated pressure calibration, the consistency between ultrasonic, dynamic, and static measurements of the equations of state is improved for these six equations of state. This consistency allows us to test the predictive power of density functional theory, with different approximations, for equation-of-state calculations. For example, the generalized gradient approximation leads to very accurate results, except for gold, the heaviest element.

Equations of state of six metals above 94 GPa

Earth’s core is structured in a solid inner core, mainly composed of iron, and a liquid outer core. The temperature at the inner core boundary is expected to be close to the melting point of iron at 330 gigapascal (GPa). Despite intensive experimental and theoretical efforts, there is little consensus on the melting behavior of iron at these extreme pressures and temperatures. We present static laser-heated diamond anvil cell experiments up to 200 GPa using synchrotron-based fast x-ray diffraction as a primary melting diagnostic. When extrapolating to higher pressures, we conclude that the melting temperature of iron at the inner core boundary is 6230 ± 500 kelvin. This estimation favors a high heat flux at the core-mantle boundary with a possible partial melting of the mantle.

https://science.sciencemag.org/content/sci/340/6131/464.full.pdf

Melting of Iron at Earth’s Inner Core Boundary Based on Fast X-ray Diffraction

Diamond is the archetypal covalent material. Each atom in an sp3 configuration is bonded to four nearest neighbours. Because of its remarkable properties, diamond has been extensively studied1. And yet our knowledge of the properties of diamond under very high pressure is still incomplete. Although diamond is known to be the preferred allotrope of carbon at high pressure, the possibility of producing under pressure high-density polymorphs of diamond, including metallic forms, has been discussed2,3,4. Structural changes have already been reported in diamond under non-hydrostatic pressures around 150 GPa and large deformation5. However, measurements6,7,8 of the properties of diamond under hydrostatic pressure have been limited to below 40 GPa. Here, we report accurate measurements of the volume and of the optical phonon frequency of diamond under hydrostatic pressure up to 140 GPa. We show that diamond is more compressible than currently expected. By combining the volume and the frequency pressure shifts, we deduce that diamond remains very stable under pressure: it is a Gruneisen solid up to at least 140 GPa, and the covalent bond is even slightly strengthened under pressure. Finally, the optical phonon frequency versus pressure is calibrated here to be used as a pressure gauge for diamond anvil cell studies in the multi-megabar range.

Properties of diamond under hydrostatic pressures up to 140 GPa.

The ambient temperature equations of state (EoS) of iron, cobalt, nickel, zinc, molybdenum, and silver have been measured by x-ray diffraction. These transition metals were compressed using diamond anvil cells with a helium pressure transmitting medium. The maximum pressure reached during these experiments varied between 65 GPa (for cobalt) and 200 GPa (for iron). This work completes previous measurements on six other metals [Phys. Rev. B 70, 094112 (2004)] to quantify the differences between ab initio calculations and experiment on a large experimental set of transition metals. The compression curves of iron, cobalt, nickel, zinc, molybdenum, silver, platinum, and gold are also calculated ab initio within the density-functional theory (DFT) formalism using the projector augmented-wave (PAW) method and different exchange-correlation functionals (LDA, GGA-PBE, GGA-PBEsol). The difference between PAW and available all-electron calculations is found to be negligible up to very high pressures. The success of each exchange-correlation functional is correlated with the atomic number. For all metals, the bulk modulus becomes overestimated at high pressure. In addition, this extended data set of metals' EoS enables to reduce further, but marginally, the systematic uncertainty of the high-pressure metrology based on the ruby standard.

Compression curves of transition metals in the Mbar range: Experiments and projector augmented-wave calculations

The compression curve of iron is measured up to 205 GPa at 298 K, under quasihydrostatic conditions in a diamond anvil cell. Above 150 GPa, the compression of this metal is significantly higher than previously measured under nonhydrostatic conditions. The same compression curve is also calculated ab initio and the deviation between experiment and theory is clearly established. A formulation of the equation of state of iron over a large pressure and temperature range, based on the current data and existing shock-wave data, is also proposed. Implications for the Earth's core are discussed.

Paul Loubeyre

Papers

Equations of state of six metals above 94 GPa

Melting of Iron at Earth’s Inner Core Boundary Based on Fast X-ray Diffraction

Properties of diamond under hydrostatic pressures up to 140 GPa.

Compression curves of transition metals in the Mbar range: Experiments and projector augmented-wave calculations

Quasihydrostatic equation of state of iron above 2 Mbar.