arXiv subjects

Ronald E. Cohen

Publications and source records attributed to Ronald E. Cohen.

At least 19 recordsLinked to original sources

arXiv2025

A Piezoelectric Molecular Cocrystal with Unconventional $π$-Stacking

We demonstrate the crystallization of a polar octafluoronaphthalene (OFN, \OFN)--phthalazine (Phth, \Phth) cocrystal, formed in a 1:2 ratio by slow evaporation. The crystal structure and vibrational properties of the cocrystal were determined using powder/single-crystal X-ray diffraction (XRD) and Fourier-Transform Infrared (FTIR) spectroscopy, and confirmed with density functional theory (DFT) and density functional perturbation theory (DFPT) calculations. The molecular $π$-stacking of aromatic rings is unconventional compared with other arene--perfluoroarene cocrystals. Phth molecules are offset and misaligned with respect to the major axis of OFN due to electrostatic repulsion between N and F atoms, enabling overall electric polarization attributed to the dipole moment of Phth. Our calculations show that OFN:2Phth is an insulator with a band gap of $\sim$2.4 eV. The electric polarization was calculated to be 7.1 \muC, while the shear piezoelectric coefficient ($d_{34}$) may be as large as 11.4 pC N$^{-1}$.

cond-mat.mtrl-sci↗

arXiv2021

Ultra-high pressure disordered eight-coordinated phase of Mg$_2$GeO$_4$: Analogue for super-Earth mantles

Mg2GeO4 is an analogue for the ultra-high pressure behavior of Mg2SiO4, so we have investigated magnesium germanate to 275 GPa and over 2000 K using a laser-heated diamond anvil cell combined with in situ synchrotron X-ray diffraction and density functional theory (DFT) computations. The experimental results are consistent with a novel phase with disordered Mg and Ge, in which germanium adopts eight-fold coordination with oxygen: the cubic Th3P4- type structure. Simulations using the special quasirandom structure (SQS) method suggest partial order in the tetragonal I-42d structure, indistinguishable from I-43d Th3P4 in our experiments. These structures have not been reported before in any oxide. If applicable to silicates, the formation of this highly coordinated and intrinsically disordered phase would have important implications for the interior mineralogy of large, rocky extrasolar planets.

cond-mat.mtrl-sci↗

arXiv2019

The Equation of State of MH-III: a possible deep CH$_4$ reservoir in Titan, Super-Titan exoplanets and moons

We investigate the thermal equation of state, bulk modulus, thermal expansion coefficient, and heat capacity of MH-III (CH$_4$ filled-ice Ih), needed for the study of CH$_4$ transport and outgassing for the case of Titan and super-Titans. We employ density functional theory and ab initio molecular dynamics simulations in the generalized-gradient approximation with a van der Waals functional. We examine the finite temperature range of $300$K-$500$K and pressures between $2$GPa-$7$GPa. We find that in this P-T range MH-III is less dense than liquid water. There is uncertainty in the normalized moment of inertia (MOI) of Titan; it is estimated to be in the range of $0.33-0.34$. If Titan's MOI is $0.34$, MH-III is not stable at present in Titan's interior, yielding an easier path for the outgassing of CH$_4$. However, for an MOI of $0.33$, MH-III is thermodynamically stable at the bottom of a ice-rock internal layer capable of storing CH$_4$. For rock mass fractions $\lessapprox 0.2$ upwelling melt is likely hot enough to dissociate MH-III along its path. For super-Titans considering a mixture of MH-III and ice VII, melt is always positively buoyant if the H$_2$O:CH$_4$ mole fraction is $>5.5$. Our thermal evolution model shows that MH-III may be present today in Titan's core, confined to a thin ($\approx 10$km) outer shell. We find that the heat capacity of MH-III is higher than measured values for pure water-ice, larger than heat capacity often adopted for ice-rock mixtures with implications for internal heating.

astro-ph.EP↗

arXiv2016

Caloric Effects in Methylammonium Lead Iodide from Molecular Dynamics Simulations

Organic-inorganic hybrid perovskite architecture could serve as a robust platform for materials design to realize functionalities beyond photovoltaic applications. We explore caloric effects in organometal halide perovskites, taking methylammonium lead iodide (MAPbI$_3$) as an example, using all-atom molecular dynamics simulations with a first-principles based interatomic potential. The adiabatic thermal change is estimated directly by introducing different driving fields in the simulations. We find that MAPbI$_3$ exhibits both electrocaloric and mechanocaloric effects at room temperature. Local structural analysis reveals that the rearrangement of molecular cations in response to electric and stress fields is responsible for the caloric effects. The enhancement of caloric response could be realized through strain engineering and chemical doping.

cond-mat.mtrl-sci↗

arXiv2012

Pressure tuning of Fermi surface topology of optimally doped BaFe$_{1.9}$Ni$_{0.1}$As$_{2}$

The superconducting, transport, and structural properties of optimally electron-doped BaFe$_{1.9}$Ni$_{0.1}$As$_{2}$ are investigated by combining the electrical resistance and synchrotron X-ray diffraction measurements at high pressures. The superconducting transition temperature of this system is found to decrease in a similar way of the axial ratio of $c/a$ with increasing pressure but vanishing at a critical pressure of 7.5 GPa where $c/a$ has a dip and an isostructural transformation from a tetragonal to a collapsed tetragonal phase takes place. The resistance is found to obey a linear temperature dependence, evidencing the antiferromagnetic spin-fluctuations transport mechanism. The pressure effects are interpreted within the framework of pressure-induced Fermi surface topology modification in which pressure suppresses both the quasiparticle effective mass and the strength of the antiferromagnetic spin fluctuations leading to the reduction of superconductivity, accordingly. The absent superconductivity in the collapsed tetragonal phase is suggested to result from the complete suppression of the antiferromagnetic spin fluctuations.

cond-mat.supr-con↗

arXiv2006

Theoretical determination of the Raman spectra of MgSiO3 perovskite and post-perovskite at high pressure

We use the density functional perturbation theory to determine for the first time the pressure evolution of the Raman intensities for a mineral, the two high-pressure structures of MgSiO3 perovskite and post-perovskite. At high pressures, the Raman powder spectra reveals three main peaks for the perovskite structure and one main peak for the post-perovskite structure. Due to the large differences in the spectra of the two phases Raman spectroscopy can be used as a good experimental indication of the phase transition.

cond-mat.mtrl-sci↗

arXiv2006

A More Accurate Generalized Gradient Approximation for Solids

We present a new nonempirical density functional generalized gradient approximation (GGA) that gives significant improvements for lattice constants, crystal structures, and metal surface energies over the most popular Perdew-Burke-Ernzerhof (PBE) GGA. The new functional is based on a diffuse radial cutoff for the exchange-hole in real space, and the analytic gradient expansion of the exchange energy for small gradients. There are no adjustable parameters, the constraining conditions of PBE are maintained, and the functional is easily implemented in existing codes.

cond-mat.mtrl-sci↗

arXiv2005

Pressure-Induced Anomalous Phase Transitions and Colossal Enhancement of Piezoelectricity in PbTiO$_3$

We find an unexpected tetragonal-to-monoclinic-to-rhombohedral-to-cubic phase transition sequence induced by pressure, and a morphotropic phase boundary in a pure compound using first-principles calculations. Huge dielectric and piezoelectric coupling constants occur in the transition regions, comparable to those observed in the new complex single-crystal solid-solution piezoelectrics such as Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_{3}$-PbTiO$_{3}$, which are expected to revolutionize electromechanical applications. Our results show that morphotropic phase boundaries and giant piezoelectric effects do not require intrinsic disorder, and open the possibility of studying this effect in simple systems.

cond-mat.mtrl-sci↗

arXiv2004

Trends in Elasticity and Electronic Structure of Transition-Metal Nitrides and Carbides from First Principles

The elastic properties of the $B_1$-structured transition-metal nitrides and their carbide counterparts are studied using the {\it ab initio\} density functional perturbation theory. The linear response results of elastic constants are in excellent agreement with those obtained from numerical derivative methods, and are also consistent with measured data. We find the following trends: (1) Bulk moduli $B$ and tetragonal shear moduli $G^{\prime}=(C_{11}-C_{12})/2$, increase and lattice constants $a_{0}$ decrease rightward or downward on the Periodic Table for the metal component or if C is replaced by N; (2) The inequality $B > G^{\prime} > G > 0$ holds for $G=C_{44}$; (3) $G$ depends strongly on the number of valence electrons per unit cell ($Z_{V}$). From the fitted curve of $G$ as a function of $Z_{V}$, we can predict that MoN is unstable in $B_{1}$ structure, and transition-metal carbonitrides ($e.g.$ ZrC$_{x}$N$_{1-x}$) and di-transition-metal carbides ($e.g.$ Hf$_{x}$Ta$_{1-x}$C) have maximum $G$ at $Z_{V} \approx 8.3$.

cond-mat.mtrl-sci↗

arXiv2002

First Principles Force Field for Metallic Tantalum

We propose a general strategy to develop accurate Force Fields (FF) for metallic systems derived from ab initio quantum mechanical (QM) calculations; we illustrate this approach for tantalum. As input data to the FF we use the linearized augmented plane wave method (LAPW) with the generalized gradient approximation (GGA) to calculate: (i) the zero temperature equation of state (EOS) of Ta for bcc, fcc, and hcp crystal structures for pressures up to ~500 GPa. (ii) Elastic constants. (iii) We use a mixed-basis pseudopotential code to calculate volume relaxed vacancy formation energy also as a function of pressure. In developing the Ta FF we also use previous QM calculations of: (iv) the equation of state for the A15 structure. (v) the surface energy bcc (100). (vi) energetics for shear twinning of the bcc crystal. We find that withappropriate parameters an embedded atom model force field (denoted as qEAM FF) is able to reproduce all this QM data. Thus, the same FF describes with good accuracy the bcc, fcc, hcp and A15 phases of Ta for pressures from ~ -10 GPa to \~ 500 GPa, while also describing the vacancy, surface energy, and shear transformations. The ability of this single FF to describe such a range of systems with a variety of coordinations suggests that it would be accurate for describing defects such as dislocations, grain boundaries, etc. We illustrate the use of the qEAM FF with molecular dynamics to calculate such finite temperature properties as the melting curve up to 300 GPa; we obtain a zero pressure melting temperature of T_{melt}=3150 +/- 50 K in good agreement with experiment (3213-3287 K). We also report on the thermal expansion of Ta in a wide temperature range; our calculated thermal expansivity agrees well with experimental data.

cond-mat.mtrl-sci↗

arXiv2001

Pressure-volume-temperature equation of state of MgSiO3 perovskite from molecular dynamics and constraints on lower mantle composition

The composition of the lower mantle can be investigated by examining densities and seismic velocities of compositional models as functions of depth. In order to do this it is necessary to know the volumes and thermoelastic properties of the compositional constituents under lower mantle conditions. We determined the thermal equation of state (EOS) of MgSiO3 perovskite using the nonempirical variational induced breathing (VIB) interatomic potential with molecular dynamics simulations at pressures and temperatures of the lower mantle. We fit our pressure-volume-temperature results to a thermal EOS of the form P(V,T) = P0(V,T0) + Delta Pth(T), where T0 = 300 K and P0 is the isothermal Universal EOS. The thermal pressure Delta Pth can be represented by a linear relationship Delta Pth = a + b T. We find V0 = 165.40 A^3, KT0 = 273 GPa, K'T0 = 3.86, a = -1.99 GPa, and b = 0.00664 GPa K^-1 for pressures of 0-140 GPa and temperatures of 300-3000 K. By fixing V0 to the experimentally determined value of 162.49 A^3 and calculating density and bulk sound velocity profiles along a lower mantle geotherm we find that the lower mantle cannot consist solely of (Mg,Fe)SiO3 perovskite with XMg ranging from 0.9-1.0. Using pyrolitic compositions of 67 vol % perovskite (XMg = 0.93-0.96) and 33 vol % magnesiowustite (XMg = 0.82-0.86), however, we obtained density and velocity profiles that are in excellent agreement with seismological models for a reasonable geotherm.

physics.geo-ph↗

arXiv2000

Accuracy of equation of state formulations

The accuracy of equation-of-state formulations is compared for theoretical total energies or experimental pressure-volume measurements for H$_{2}$, Ne, Pt, and Ta. This spans the entire range of compression found for minerals and vo latiles in the Earth. The Vinet equation is found to be most accurate. The origin of the behavior of different equation-of-state formulations is discussed. It is shown that subtle phase transitions can be detected by examining the residuals from an equation-of-state fit. A change in the electronic structure of Ta is found at high pressures using this procedure, and a possible new transition in H$_{2}$.

cond-mat.mtrl-sci↗

arXiv2000

Thermal Equation of State of Tantalum

We have investigated the thermal equation of state of tantalum from first principles using the Linearized Augmented Plane Wave (LAPW) and pseudopotential methods for pressures up to 300 GPa and temperatures up to 10000 K. The equation of state at zero temperature was computed using LAPW. For finite temperatures, mixed basis pseudopotential computations were performed for 54 atom supercells. The vibrational contributions were obtained by computing the partition function using the particle in a cell model, and the the finite temperature electronic free energy was obtained from the LAPW band structures. We discuss the behavior of thermal equation of state parameters such as the Grüneisen parameter $γ$, $q$, the thermal expansivity $α$, the Anderson-Grüneisen parameter $δ_T$ as functions of pressure and temperature. The calculated Hugoniot shows excellent agreement with shock-wave experiments. An electronic topological transition was found at approximately 200 GPa.

cond-mat.mtrl-sci↗

arXiv2000

Absence of lattice strain anomalies at the electronic topological transition in zinc at high pressure

High pressure structural distortions of the hexagonal close packed (hcp) element zinc have been a subject of controversy. Earlier experimental results and theory showed a large anomaly in lattice strain with compression in zinc at about 10 GPa which was explained theoretically by a change in Fermi surface topology. Later hydrostatic experiments showed no such anomaly, resulting in a discrepancy between theory and experiment. We have computed the compression and lattice strain of hcp zinc over a wide range of compressions using the linearized augmented plane wave (LAPW) method paying special attention to k-point convergence. We find that the behavior of the lattice strain is strongly dependent on k-point sampling, and with large k-point sets the previously computed anomaly in lattice parameters under compression disappears, in agreement with recent experiments.

cond-mat.mtrl-sci↗

arXiv1999

Theory of ferroelectrics: A vision for the next decade and beyond

In the last ten years significant advances have been made in our understanding and ability to compute and predict properties of ferroelectrics and piezoelectrics using fundamental physics. Phase diagrams, electromechanical and elastic properties, and effects of defects and surfaces are now amenable to computation. Most importantly, new techniques have been developed, and new understanding of the meaning of polarization in dielectrics has been developed. Prospects for the future are discussed.

cond-mat.mtrl-sci↗

arXiv1997

Thermal Conductivity of MgO at High Pressures

The first non-empirical computation of lattice thermal conductivity has been performed for MgO using molecular dynamics (MD), a non-empirical ionic model (the Variationally Induced Breathing (VIB) model), and Green-Kubo theory. The computation is first-principles in the sense that no parameters are fit to experiment. Results are presented at low pressure as a function of temperature, and for 2500K for pressures to 290 GPa. We find an unexpectedly small pressure effect at small compressions, perhaps due to saturation of thermal conductivity at the high temperatures due to the small mean free path. At higher pressure expected behavior is found.

cond-mat.mtrl-sci↗

arXiv1997

Effects of pressure on diffusion and vacancy formation in MgO from non-empirical free-energy integrations

The free energies of vacancy pair formation and migration in MgO were computed via molecular dynamics using free-energy integrations and a non-empirical ionic model with no adjustable parameters. The intrinsic diffusion constant for MgO was obtained at pressures from 0 to 140 GPa and temperatures from 1000 to 5000 K. Excellent agreement was found with the zero pressure diffusion data within experimental error. The homologous temperature model which relates diffusion to the melting curve describes well our high pressure results within our theoretical framework.

cond-mat.mtrl-sci↗

arXiv1997

Surface Effects in Ferroelectrics: Periodic Slab Computations for BaTiO_3

Total energies, electronic structure, surface energies, polarization, potentials and charge densities were studied for slabs of BaTiO_3 using the Linearized Augmented Plane Wave (LAPW) method. The depolarization field inhibits ferroelectricity in the slabs, and the macroscopic field set up across a ferroelectric slab is sufficient to cause electronic states to span the gap and give a metallic band structure, but the band shifts are not rigid and O p states tend to pile up at the Fermi level. There are electronic surface states, especially evident on TiO_2 surfaces. The dangling bonds bond back to the surface Ti's and make the surface stable and reactive. The BaO surfaces are more ionic than the bulk.

mtrl-th↗