19 research outputs found
Crystal Structure Evolution of Fluorine under High Pressure
Fluorinated compounds in the last decade were applied as photo-thermo-refractive glasses, high-stress lubricants, and pharmaceutical drugs due to their good mechanical properties and biocompatibility. Although fluorinated materials are largely employed, the possibility of predicting new structures was limited by the impossibility to use density functional theory (DFT) to describe interatomic and intermolecular interactions correctly. This is seen linearly to increase with fluorine concentration. In crystal structure prediction, modern algorithms are usually combined with first-principles methods employed for global solution, which sometimes fail to describe systems as in the case of strongly correlated materials. Fluorine is one of the tricky elements, which is characterized by relativistic effects and no overlap between the DFT exchange hole and the exact exchange hole. Thus, no relativistic exchangeâcorrelation functional was seen to adequately describe fluorine. In this work, we have found an excellent compromise to investigate fluorinated materials using a combination of SCAN (exchange) and rVV10 (correlation) functionals. This was found through the fundamental study of α- and ÎČ-fluorine phases, showing α-fluorine as the most stable structure at temperatures lower than 35 K and 0 GPa with respect to ÎČ-fluorine. Further, we have computed crystal structure evolution under pressure looking for new stable fluorine allotropes using the USPEX evolutionary algorithm coupled with the SCAN-rVV10 exchangeâcorrelation functional discovering two phase transitions: one from C2/c (i.e., α-fluorine) to Cmca at âŒ5.5 GPa and from Cmca to the P4Ì
21c phase at 220 GPa; all these structures possess metallic behavior. The achievements of this work lie far beyond the thermodynamic of fluorine crystals under pressure. It will give the right instrument to understand the chemical behavior of fluorinated materials under pressure with consequent great speed up to the crystal structure prediction of fluorinated and fluorine-based materials
Crystal Structure Evolution of Fluorine under High Pressure
Fluorinated compounds in the last decade were applied as photothermo-refractive glasses, high-stress lubricants, and pharmaceutical drugs due to their
good mechanical properties and biocompatibility. Although fluorinated materials are
largely employed, the possibility of predicting new structures was limited by the
impossibility to use density functional theory (DFT) to describe interatomic and
intermolecular interactions correctly. This is seen linearly to increase with fluorine
concentration. In crystal structure prediction, modern algorithms are usually
combined with first-principles methods employed for global solution, which
sometimes fail to describe systems as in the case of strongly correlated materials.
Fluorine is one of the tricky elements, which is characterized by relativistic effects and no overlap between the DFT exchange hole
and the exact exchange hole. Thus, no relativistic exchangeâcorrelation functional was seen to adequately describe fluorine. In this
work, we have found an excellent compromise to investigate fluorinated materials using a combination of SCAN (exchange) and
rVV10 (correlation) functionals. This was found through the fundamental study of α- and ÎČ-fluorine phases, showing α-fluorine as
the most stable structure at temperatures lower than 35 K and 0 GPa with respect to ÎČ-fluorine. Further, we have computed crystal
structure evolution under pressure looking for new stable fluorine allotropes using the USPEX evolutionary algorithm coupled with
the SCAN-rVV10 exchangeâcorrelation functional discovering two phase transitions: one from C2/c (i.e., α-fluorine) to Cmca at
âŒ5.5 GPa and from Cmca to the P4Ì
21c phase at 220 GPa; all these structures possess metallic behavior. The achievements of this
work lie far beyond the thermodynamic of fluorine crystals under pressure. It will give the right instrument to understand the
chemical behavior of fluorinated materials under pressure with consequent great speed up to the crystal structure prediction of
fluorinated and fluorine-based materials
Generating and grading 34 Optimised Norm-Conserving Vanderbilt Pseudopotentials for Actinides and Super Heavy Elements in the PseudoDojo
In the last decades, material discovery has been a very active research field
driven by the necessity of new materials for different applications. This has
also included materials incorporating heavy elements, beyond the stable
isotopes of lead. Most of actinides exhibit unique properties that make them
useful in various applications. Further, new heavy elements, taking the name of
super-heavy elements, have been synthesized, filling previously empty space of
Mendeleev periodic table. Their chemical bonding behaviour, of academic
interest at present, would also benefit of state-of-the-art modelling
approaches. In particular, in order to perform first-principles calculations
with planewave basis sets, one needs corresponding pseudopotentials. In this
work, we present a series of fully-relativistic optimised norm-conserving
Vanderbilt pseudopotentials (ONCVPs) for thirty-four actinides and super-heavy
elements. The scalar relativistic version of these ONCVPs is tested by
comparing equations of states for crystals, obtained with \textsc{abinit} 9.6,
with those obtained by all-electron zeroth-order regular approximation (ZORA)
calculations performed with the Amsterdam Modelling Suite BAND code.
-Gauge and -Gauge indicators are used to validate these
pseudopotentials. This work is a contribution to the PseudoDojo project, in
which pseudopotentials for the whole periodic table are developed and
systematically tested. The fully-relativistic pseudopotential files (i.e.
including spin-orbit coupling) are available on the PseudoDojo web-interface
pseudo-dojo.org under the name NC FR (ONCVPSP) v4.x. Pseudopotentials are made
available in psp8 and UPF2 formats, both convenient for \textsc{abinit}, the
latter being also suitable for Quantum ESPRESSO
Constrained Density Functional Theory: A Potential-Based Self-Consistency Approach
Chemical reactions, charge transfer reactions, and
magnetic materials are notoriously difficult to describe within
KohnâSham density functional theory, which is strictly a groundstate technique. However, over the last few decades, an
approximate method known as constrained density functional
theory (cDFT) has been developed to model low-lying excitations
linked to charge transfer or spin fluctuations. Nevertheless, despite
becoming very popular due to its versatility, low computational
cost, and availability in numerous software applications, none of the
previous cDFT implementations is strictly similar to the
corresponding ground-state self-consistent density functional
theory: the target value of constraints (e.g., local magnetization)
is not treated equivalently with atomic positions or lattice
parameters. In the present work, by considering a potential-based formulation of the self-consistency problem, the cDFT is
recast in the same framework as KohnâSham DFT: a new functional of the potential that includes the constraints is proposed, where
the constraints, the atomic positions, or the lattice parameters are treated all alike, while all other ingredients of the usual potentialbased DFT algorithms are unchanged, thanks to the formulation of the adequate residual. Tests of this approach for the case of spin
constraints (collinear and noncollinear) and charge constraints are performed. Expressions for the derivatives with respect to
constraints (e.g., the spin torque) for the atomic forces and the stress tensor in cDFT are provided. The latter allows one to study
striction effects as a function of the angle between spins. We apply this formalism to body-centered cubic iron and first reproduce the
well-known magnetization amplitude as a function of the angle between local magnetizations. We also study stress as a function of
such an angle. Then, the local collinear magnetization and the local atomic charge are varied together. Since the atomic spin
magnetizations, local atomic charges, atomic positions, and lattice parameters are treated on an equal footing, this formalism is an
ideal starting point for the generation of model Hamiltonians and machine-learning potentials, computation of second or third
derivatives of the energy as delivered from density-functional perturbation theory, or for second-principles approaches
Hardness Descriptor Derived from Symbolic Regression
Hard and superhard materials play a vital role in numerous industrial
applications necessary for sustainable development. However, discovering new
materials with high hardness is challenging due to the complexity of this
multiscale property and its and its intricate relationship with the atomic
properties of the material. Here, we introduce a low-dimensional physical
descriptor for Vickers hardness derived from a symbolic-regression artificial
intelligence approach to data analysis. This descriptor is a mathematical
combination of materials' properties that can be evaluated much more easily
than hardness itself through the atomistic simulations, therefore suitable for
a high-throughput screening. The artificial intelligence model was developed
and trained using the experimental hardness values and high-throughput
screening was performed on 635 compounds, including binary, ternary, and
quaternary transition-metal borides, carbides, nitrides, carbonitrides,
carboborides, and boronitrides to identify the optimal superhard material. The
proposed descriptor is a physically interpretable analytic formula that
provides insight into the multiscale relationship between atomic structure
(micro) and hardness (macro). We discovered that hardness is proportional to
the Voigt-averaged bulk modulus and inversely proportional to the Poisson's
ratio and Reuss-averaged shear modulus. Results of high-throughput search
suggest the enhancement of material hardness through mixing with harder, yet
metastable structures (e.g., metastable VN, TaN, ReN, CrN, and
ZrB, all of them exhibit high hardness)
Electronic Properties of Functionalized Diamanes for Field-Emission Displays
Ultrathin diamond films, or diamanes, are promising quasi-2D materials that are
characterized by high stiffness, extreme wear resistance, high thermal conductivity, and chemical
stability. Surface functionalization of multilayer graphene with different stackings of layers could
be an interesting opportunity to induce proper electronic properties into diamanes. Combination
of these electronic properties together with extraordinary mechanical ones will lead to their
applications as field-emission displays substituting original devices with light-emitting diodes or
organic light-emitting diodes. In the present study, we focus on the electronic properties of
fluorinated and hydrogenated diamanes with (111), (110), (0001), (101Ì
0), and (2Ì
110)
crystallographic orientations of surfaces of various thicknesses by using first-principles calculations
and Bader analysis of electron density. We see that fluorine induces an occupied surface electronic
state, while hydrogen modifies the occupied bulk state and also induces unoccupied surface states.
Furthermore, a lower number of layers is necessary for hydrogenated diamanes to achieve the convergence of the work function in
comparison with fluorinated diamanes, with the exception of fluorinated (110) and (2Ì
110) films that achieve rapid convergence and
have the same behavior as other hydrogenated surfaces. This induces a modification of the work function with an increase of the
number of layers that makes hydrogenated (2Ì
110) diamanes the most suitable surface for field-emission displays, better than the
fluorinated counterparts. In addition, a quasi-quantitative descriptor of surface dipole moment based on the TantardiniâOganov
electronegativity scale is introduced as the average of bond dipole moments between the surface atoms. This new fundamental
descriptor is capable of predicting a priori the bond dipole moment and may be considered as a new useful feature for crystal
structure prediction based on artificial intelligence
Translucency and Color Stability of a Simplified Shade Nanohybrid Composite after Ultrasonic Scaling and Air-Powder Polishing
We aimed to assess the influence of professional dental prophylaxis on the translucency
and color stability of a novel simplified shade nanohybrid composite material. Sixty composite
disks (5 mm in diameter and 2 mm thick) of light (n = 30) and dark (n = 30) shades were prepared.
The specimens were randomly divided into the following three groups (n = 10) according to the
prophylaxis procedure used: ultrasonic scaling, air-powder polishing with sodium bicarbonate, and
controls. The specimens were submitted to translucency and color analysis based on the CIELab
system. Two measurements were performed before and after 48-h storage in coffee. Translucency
values of untreated light and dark specimens were 9.15 ± 0.38 and 5.28 ± 1.10, respectively. Airpowder polishing decreased the translucency of the light composite specimens. Storage in coffee
resulted in color changes (âE) ranging between 2.69 and 12.05 and a mean translucency decrease
ranging between â0.88 and â6.91. The samples in the light group tended to exhibit greater staining;
the treatment method had no effect on âE. It can be concluded that light-shade composite restorations
are more prone to translucency and color changes resulting from air-powder polishing and contact
with staining media. However, further research using other composites and powders is required
Sr-Doped Molecular Hydrogen: Synthesis and Properties of SrH
Recently, several research groups announced reaching the point of
metallization of hydrogen above 400 GPa. Following the mainstream of extensive
investigations of compressed polyhydrides, in this work we demonstrate that
small (4 atom %) doping of molecular hydrogen by strontium leads to a dramatic
reduction in the metallization pressure to about 200 GPa. Studying the
high-pressure chemistry of the Sr-H system at 56-180 GPa, we observed the
formation of several previously unknown compounds: C2/m-SrH,
pseudocubic SrH, SrH with cubic F-43m Sr sublattice, and
pseudotetragonal P1-SrH, the metal hydride with the highest hydrogen
content discovered so far. Unlike Ca and Y, strontium forms molecular
semiconducting polyhydrides, whereas calcium and yttrium polyhydrides are
high-Tc superconductors with an atomic H sublattice. The latter phase,
SrH or SrH, may be considered as a convenient model of
the consistent bandgap closure and metallization of hydrogen. Using the
impedance measurements in diamond anvil cells at 300-440 K, we estimated the
direct bandgap of the Pm-3n-like compound P1-SrH to be 0.44-0.51 eV at 150
GPa, and its metallization pressure to be 220 GPa. Together with the machine
learning interatomic potentials, the impedance spectroscopy allowed us to
estimate the diffusion coefficients of hydrogen D = 1.0-2.8 E-10 m/s in
SrH and 1.2-2.1 E-9 m/s in P1-SrH at 500-600 K.Comment: Supporting information was compressed and reduced by 2 times to 36
figure
Band gap bowing and spectral width of Ga(1âx)InxN alloys for modelling light emitting diodes
Ga(1â)InN alloys, widely employed to produce light-emitting diodes, exhibit a bowing of the band gap as a function of concentration , and a luminescence spectral width which differs from the expected value of 1.8 kT. Through first-principles calculations, based on many-body perturbation theory and density-functional theory with a meta-GGA exchangeâcorrelation functional, we explore jointly these effects, in an exhaustive set of Ga(1â)InN supercells with 16 atoms. We disentangle the bowing due to the average volume change with the one due local atomic configuration and local relaxation. The first one account for about 40% of the bowing, despite that fact that the change of volume with respect to concentration is nearly linear (Vegardâs law). The computed bowing parameter is 1.39 eV. The experimental broadening between 3 kT and 8 kT, not examined theoretically until now, is well accounted by local atomic configuration changes and lifting of the degeneracy of the top of the valence band