Ling-Cang Cai

Theoretical investigation of the high pressure structure, lattice dynamics, phase transition, and thermal equation of state of titanium metal

We report a detailed first-principles calculation to investigate the structures, elastic constants, and phase transition of Ti. The axial ratios of both alpha-Ti and omega-Ti are nearly constant under hydrostatic compression, which confirms the latest experimental results. From the high pressure elastic constants, we find that the alpha-Ti is unstable when the applied pressures are larger than 24.2 GPa, but the omega-Ti is mechanically stable at all range of calculated pressure. The calculated phonon dispersion curves agree well with experiments. Under compression, we captured a large softening around Gamma point of alpha-Ti. When the pressure is raised to 35.9 GPa, the frequencies around the Gamma point along Gamma-M-K and Gamma-A in transverse acoustical branches become imaginary, indicating a structural instability. Within quasiharmonic approximation, we obtained the full phase diagram and accurate thermal equations of state of Ti. The phase transition omega-Ti ->alpha-Ti ->beta-Ti at zero pressure occurs at 146 K and 1143 K, respectively. The predicted triple point is at 9.78 GPa, 931 K, which is close to the experimental data. Our thermal equations of state confirm the available experimental results and are extended to a wider pressure and temperature range

Ab initio investigation of the lower energy candidate structures for (H2O)5+ water cluster

The particle swarm optimization method in conjunction with density functional calculations is used to search the lower energy structures for the cationic water clusters (H2O)5(+). Geometry optimization, vibrational analysis, and infrared spectrum calculation are performed for the most interesting clusters at the MP2/aug-cc-pVDZ level. The relationships between their structural arrangements and their energies are discussed. According to their relative Gibbs free energies, their energy order is determined and four lowest energy isomers are found to have a relative population surpassing 1% below 350 K. Studies reveal that, among these four isomers, one new cluster found here also contributes a lot to the experimental infrared spectrum. Based on topological analysis and reduced density gradient analysis, some meaningful points are found by studying the structural characteristics and the bonding strengths of these cationic water clusters: in the first solvation shell, the central H3O(+) motifs may have a stronger interaction with the OH radical than with the water molecules. The interaction in the second solvation shell may also be stronger than that in the first solvation shell, which is opposite to our intuition.

Lattice Dynamics and Thermodynamics of Molybdenum from First-Principles Calculations

We calculated the phase transition, elastic constants, full phonon dispersion curves, and thermal properties of molybdenum (Mo) for a wide range of pressures using density functional theory. Mo is stable in the body-centered-cubic (bcc) structure up to 703 +/- 19 GPa and then transforms to the face-centered close-packed (fcc) structure at zero temperature. Under high temperature and pressure, the fcc phase of Mo is more stable than the bcc phase. The calculated phonon dispersion curves accord excellently with experiments. Under pressure, we captured a large softening along H-P in the TA branches. When the volume is compressed to 7.69 A(3), the frequencies along H-P in the TA branches soften to imaginary frequencies, indicating a structural instability. When the pressure increases, the phonon calculations on the fcc Mo predict the stability by promoting the frequencies along Gamma to X and Gamma to L symmetry lines from imaginary to real. The thermal equation of state was also investigated. From the thermal expansion coefficient and the heat capacity, we found that the quasiharmonic approximation was valid only up to about melting point at zero pressure. However, under pressure, the validity can be extended to a much higher temperature.

Ab initio calculation of lattice dynamics and thermodynamic properties of beryllium

We investigate the phase transition, elastic constants, phonon dispersion curves, and thermal properties of beryllium (Be) at high pressures and high temperatures using density functional theory. By comparing the Gibbs free energy, in the quasiharmonic approximation (QHA), of hexagonal-closed-packed (hcp) with those of the face-centered cubic (fcc) and body-centered-cubic (bcc) we find that the hcp Be is stable up to 390 GPa, and then transforms to the bcc Be. The calculated phonon dispersion curves are in excellent agreement with experiments. Under compression, the phonon dispersion curves of hcp Be do not show any anomaly or instability. At low pressure the phonon dispersion of bcc Be display imaginary along Gamma-N in the T-1 branches. Within the quasiharmonic approximation, we predict the thermal equation of state and other properties including the thermal expansion coefficient, Hugoniot curves, heat capacity, Gruneisen parameter, and Debye temperature

Melting curves and entropy of fusion of body-centered cubic tungsten under pressure

The melting curves and entropy of fusion of body-centered cubic (bcc) tungsten (W) under pressure are investigated via molecular dynamics (MD) simulations with extended Finnis-Sinclair (EFS) potential. The zero pressure melting point obtained is better than other theoretical results by MD simulations with the embedded-atom-method (EAM), Finnis-Sinclair (FS) and modified EAM potentials, and by ab initio MD simulations. Our radial distribution function and running coordination number analyses indicate that apart from the expected increase in disorder, the main change on going from solid to liquid is thus a slight decrease in coordination number. Our entropy of fusion of W during melting, Delta S, at zero pressure, 7.619 J/mol.K, is in good agreement with the experimental and other theoretical data. We found that, with the increasing pressure, the entropy of fusion Delta S decreases fast first and then oscillates with pressure; when the pressure is higher than 100 GPa, the entropy of fusion Delta S is about 6.575 +/- 0.086 J/mol.K, which shows less pressure effect

Sound velocity measurements of tantalum under shock compression in the 10-110 GPa range

The high-pressure melting curve of tantalum (Ta) has been the center of a long-standing controversy. Sound velocities along the Hugoniot curve are expected to help in understanding this issue. To that end, we employed a direct-reverse impact technique and velocity interferometry to determine sound velocities of Ta under shock compression in the 10-110 GPa pressure range. The measured longitudinal sound velocities show an obvious kink at ∼60 GPa as a function of shock pressure, while the bulk sound velocities show no discontinuity. Such observation could result from a structural transformation associated with a negligible volume change or an electronic topological transition.

Structure and thermodynamic properties of BeO: Empirical corrections in the quasiharmonic approximation

The equilibrium lattice parameters, bulk modulus, and phase transition of BeO are investigated by using the density functional theory with the Perdew-Burke-Ernzerhof (PBE) and Perdew and Zunger (PZ) functionals. With two different exchange-correlation functionals, we predict the similar results that BeO is stable in hexagonal wurtzite (B4) phase up to pressure of 100 GPa and then transforms directly into the rocksalt (B1) phase. The calculated phonon dispersion curves of the B4 phase BeO are in excellent agreement with the experimental data. Under compression, the phonon dispersion curves of BeO in the B4 phase do not show any anomaly or instability. Within the quasiharmonic approximation (QHA) plus empirical energy corrections (EEC) calculations, the thermal equation of state and thermodynamic properties of BeO are obtained. The EECs improve the systematic deviations of PBE and PZ functionals and reproduce the experimental results in the range of the validity of the QHA. Moreover, the effect of EECs on t...

Shock compression response of a Zr-based bulk metallic glass up to 110 GPa

Shock wave compression experiments were conducted on a Zr-based bulk metallic glass (BMG, Zr51Ti5Ni10Cu25Al9 in atomic percent) up to 110 GPa. Time-resolved free-surface velocity profiles were measured in a shock stress range from 18 to 28 GPa with velocity interferometer techniques. The shock Hugoniot data in a shock stress range from 53 to 110 GPa were obtained by using electric pin techniques. The time-resolved wave profiles showed a distinct two-wave structure consisting of an elastic precursor followed by a plastic wave. Based on the obtained wave profiles, the Hugoniot elastic limits were determined to be 6.9 to 9.6 GPa. The shock wave velocity (Ds) vs. particle velocity (up) Hugoniot data in a shock stress range from 18 to 110 GPa were linearly fitted by Ds=(4.241±0.035)+(1.015±0.024)up. No evidence of phase transition was found in the performed shock experiments of the Zr-based BMG.

Magnetism and phase transitions of iron under pressure

The spin-polarized generalized gradient approximation within the plane-wave pseudopotential density functional theory is employed to investigate the magnetism and phase transition of iron under pressure. It is found that iron has a ferromagnetic body-centered-cubic (bcc) ground state, while at high pressure (such as at the Earths lower mantle and core pressure), the most stable phase is the nonmagnetic hexagonal-close-packed (hcp) phase. For the face-centered-cubic (fcc) iron, we find that there is an intermediate-spin state (IS) during the transformation from the high-spin state (HS) to the low-spin (LS) state under pressure. The transition pressures of the HS -> IS and the IS -> LS are about 15 GPa and 50 GPa, respectively. The magnetism can affect the properties of iron up to 72.9 GPa. From the enthalpy difference between every two phases, we find the phase transition pressures of FM-bcc -> FM-hcp, FM-bcc -> NM-hcp and NM-bcc -> NM-hcp are 14.4 GPa, 29.5 GPa and 42.7 GPa, respectively.

Dumbbell silicene: a strain-induced room temperature quantum spin Hall insulator

By the generalized gradient approximation in the framework of density functional theory, we find a new silicon allotrope (called dumbbell silicene) with high stability, which can turn a quantum spin Hall insulator with an inverted band gap through tuning external compression strain, just like in previous silicene. However, the obtained maximum topological nontrivial band gap about 12 meV under isotropic strain is much larger than that for previous silicene, and can be further improved to 36 meV by tuning extra anisotropic strain, which is sufficiently large to realize quantum spin Hall effect even at room-temperature, and thus is beneficial to the fabrication of high-speed spintronics devices. Furthermore, we confirm that the boron nitride sheet is an ideal substrate for the experimental realization of the dumbbell silicene under external strain, maintaining its nontrivial topology. These properties make the two-dimensional dumbbell silicene a good platform to study novel quantum states of matter, showing great potential for future applications in modern silicon-based microelectronics industry.