Calculations Of Phonon Modes Research Articles

The impact of low-energy phonon lifetimes on the magnetic relaxation in a dysprosocenium single-molecule magnet.

Developing molecular spin technologies requires microscopic knowledge of their spin-dynamics. Calculation of phonon modes, phonon scattering and spin-phonon coupling for a dysprosocenium single-molecule magnet (SMM) give simulations of spin-dynamics that agree with experiment. They show that low-energy phonon scattering is a significant contribution to the high-performance of dysprosocenium SMMs.

Evaluating strain and doping of Janus MoSSe from phonon mode shifts supported by ab initio DFT calculations.

With the study of Janus monolayer transition metal dichalcogenides, in which one of the two chalcogen layers is replaced by another type of chalcogen atom, research on two-dimensional materials is advancing into new areas. Yet only little is known about this new kind of material class, mainly due to the difficult synthesis. In this work, we synthesize MoSSe monolayers from exfoliated samples and compare their Raman signatures with density functional theory calculations of phonon modes that depend in a nontrivial way on doping and strain. With this as a tool, we can infer limits for the possible combinations of strain and doping levels. This reference data can be applied to all MoSSe Janus samples in order to quickly estimate their strain and doping, providing a reliable tool for future work. In order to narrow down the results for our samples further, we analyze the temperature-dependent photoluminescence spectra and time-correlated single-photon counting measurements. The lifetime of Janus MoSSe monolayers exhibits two decay processes with an average total lifetime of 1.57 ns. Moreover, we find a strong trion contribution to the photoluminescence spectra at low temperature which we attribute to excess charge carriers, corroborating our ab initio calculations.

Orthorhombic C32: A topological semimetal with nodal ring

We identify by ab initio calculations a new topological semimetal with a nodal ring in an sp2-sp3 hybridized carbon network, with a 32-atom base-centered orthorhombic unit cell in Cccm (D2h20) symmetry, termed as bco-C32 carbon. The dynamical stability of bco-C32 carbon has been confirmed with phonon mode calculations and the thermal stability has been confirmed by molecular dynamics simulations. Electronic band structures calculations show that bco-C32 carbon is a topological nodal line semimetal with a closed nodal ring centering the high-symmetric Γ point inside the first Brillouin zone, and the drumhead-like topological non-trivial surface states can be seen inside or outside the projected nodal ring in the (001) surface depending on the different surface terminations. Moreover, the calculated optical properties show that bco-C32 carbon is a dark black carbon phase like as graphite. Our findings have identified a new sp2-sp3 hybridized carbon allotrope and provide insights for its physical properties.

Predicting the stability and electronic structure of alkali metal aurides

Density functional theory calculations of phonon modes predict that some compounds of the alkali metal aurides family, general formula A 2 MAu6 (A = K, Rb or Cs; M = Ti, Zr, Hf, Sn or Pb), have stable three-dimensional phase with a double perovskite-type structure and cubic Fm m space group (K2PtCl6-type). Bader’s charge analysis shows that most electron density is located within the six atoms at the octahedra vertices like double perovskite halides. However, the short spacing between Au anions enables d-orbital interactions between them. Compounds of this family, with group 4 metals only, carry conduction states around the Γ point (k = 0). On the other hand, compounds with group 14 metals possess more conduction states around all the Brillouin zone and have electron pockets in their band structures. These compounds provide further insights into the unusual anionic behavior of gold and present other alternatives for the construction of divergent nanodevices.

Topological nodal line semimetal in an all-sp 2 monoclinic carbon

Topological nodal line semimetal is an exotic class of quantum materials featuring the continuous line of nodes inside the first Brillouin zone. Here we identify by systematical ab initio calculations a new all-sp 2 hybridized carbon allotrope with monoclinic C2/c symmetry which is termed as bcm-C16. Total energy calculations show that our proposed bcm-C16 carbon is energetically comparable to or stable than the previously proposed bco-C16, bct-C16, and oP16 carbon. Its dynamical stability has been confirmed by phonon mode calculations. Detailed analysis of the electronic properties show that bcm-C16 carbon is a topological nodal line semimetal with a single closed nodal ring around the Γ high symmetric point, protected by spatial inversion and time-reversal symmetry. When the nodal ring is projected onto the (001) surface, a topologically protected drumhead-like surface state can be seen inside or outside the nodal ring depending on the different surface terminations. Moreover, we also examined the tensile-strain robustness of the electronic properties of bcm-C16 carbon. The nodal ring is robust under a tensile-strain along the crystalline x- and z-directions up to 20%. In addition, the simulated x-ray diffraction pattern (XRD) of bcm-C16 carbon matches with the experimental pattern found in the detonation and chimney soot experiment. The present proposal has enriched the family of carbon allotropes with topological nodal lines, and pave the way for further theoretical and experimental studies.

Optical Properties of Epsilon Iron Oxide Nanoparticles in the Millimeter- and Terahertz-Wave Regions

Abstract Epsilon iron oxide (ε-Fe2O3) is attracting global attention as a magnetic material with a large magnetic anisotropy. In this article, the optical properties of ε-Fe2O3 nanoparticles and the metal-substituted series of ε-MxFe2−xO3 (M = Ga, In, and Al) are studied over a wide frequency range from the millimeter-wave to terahertz-wave region, 30 GHz–30 THz, using terahertz time-domain, far-infrared, and Raman spectroscopies. To understand the spectroscopic data, first-principles calculations of the electronic structure and phonon modes are performed. First, an ε-Fe2O3 bar magnet is introduced and its atomic movements are calculated by phonon mode calculations. Second, the phonon modes of Ga-substituted ε-Fe2O3 are calculated. Far-IR, mid-IR, and Raman spectroscopies confirm that the calculated and observed spectra show good agreement. Third, the influences of In-substitution on the crystal structure, magnetic properties, and millimeter-wave absorption are described. In high-frequency millimeter-wave absorption due to magnon, the resonance frequency decreased with In-substitution. Finally, the millimeter-wave absorption property of ε-AlxFe2−xO3 is described. An absorption peak due to the natural resonance occurs at 100 GHz. The rotation data of the transmitted millimeter wave are determined by millimeter-wave–polarization-plane measurements.

Large diamagnetism and low-lying optical phonon modes in Pt–Cd γ-phase

Multi-shell polyhedral clusters appear as building blocks in the crystal structures of quasicrystals and cage compounds. The multi-shell clusters in these materials are expected to provide characteristic features in the thermal, electronic, and magnetic properties, which still remain to be clarified. To shed light on this issue, we studied the electrical transport, heat capacity, and magnetic properties of Pt0.19Cd0.81 single crystals. Specific heat measurements and ab initio calculations of phonon modes revealed that the optical modes consist of extremely low-energy T2 triplet branches at as low as ~30 K and a highly dense continuum above ~50 K. The latter can account for a crossover behavior in the temperature dependence of the electrical resistivity. In the magnetic susceptibility, an anomalously large diamagnetic contribution attributable to the electrons’ orbital motion was observed. Possible origins, including the flow of ring currents in the multi-shell clusters and interband effects near possible Dirac points, are discussed.

Electric field and strain induced gap modifications in multilayered GaN

Two-dimensional materials with a wide bandgap characteristic are critical to developing novel nanoscaled electronic devices. This study investigates the layer, in-plane biaxial strain, and vertical external electric field effects on the stability and electronic properties of multilayered GaN employing the density functional theory. Using structural optimization and phonon-mode calculations, the GaN structures with one to five layers are found to be stable and refer to the Born–Oppenheimer local minima. Under dimensionality effect, GaN unveils a semiconducting feature with an indirect bandgap at the HSE06 level that changes from 3.37eV for a monolayer to 2.79eV for a five-layered structure as the quantum confinement effect is reduced. The calculations demonstrate that the indirect bandgap of multilayered GaN decreases linearly when increasing the tensile strain. However, compressive strain engineering would induce an indirect-to-direct gap transition. Additionally, when the strength of the applied perpendicular external electric field to the multilayered GaN surface is increased, the GaN bandgap rapidly disappears due to the field-induced near free electronic gas. Calculated carrier effective mass indicate that both external effects impact charge carrier mobility as well. Such significant changes in the electronic properties under external excitations show that multilayered GaN shows promise in configurable nanoelectronic devices.

Toward Physics-Based Solubility Computation for Pharmaceuticals to Rival Informatics.

We demonstrate that physics-based calculations of intrinsic aqueous solubility can rival cheminformatics-based machine learning predictions. A proof-of-concept was developed for a physics-based approach via a sublimation thermodynamic cycle, building upon previous work that relied upon several thermodynamic approximations, notably the 2RT approximation, and limited conformational sampling. Here, we apply improvements to our sublimation free-energy model with the use of crystal phonon mode calculations to capture the contributions of the vibrational modes of the crystal. Including these improvements with lattice energies computed using the model-potential-based Ψmol method leads to accurate estimates of sublimation free energy. Combining these with hydration free energies obtained from either molecular dynamics free-energy perturbation simulations or density functional theory calculations, solubilities comparable to both experiment and informatics predictions are obtained. The application to coronene, succinic acid, and the pharmaceutical desloratadine shows how the methods must be adapted for the adoption of different conformations in different phases. The approach has the flexibility to extend to applications that cannot be covered by informatics methods.

Materials informatics approach for design of Si/Ge layered nanostructures with low thermal conductivity

We report an efficient method based on the materials informatics approach to predict low thermal conductivity structures using a descriptor obtained by phonon mode calculations. For a small number of Si/Ge layered structures, we perform normal mode analysis to calculate the participation ratio for each phonon mode and calculations of thermal conductivity in the stacking direction using the perturbed molecular dynamics (MD) method. The descriptor for the thermal conductivity is defined using the participation ratios averaged in the acoustic phonon frequency ranges with their lower and upper limits independently optimized. By employing the descriptor and genetic algorithm, low thermal conductivity structures are recommended among a huge number of possible structures. The recommended structures are confirmed to have very small thermal conductivities from the results of the perturbed MD calculations. By employing the method, we can design Si/Ge layered structures with low thermal conductivity at very low computational cost.

Low thermal conductivity of peanut-shaped carbon nanotube and its insensitive response to uniaxial strain

Motivated by the experimental synthesis of peanut-shaped carbon nanotubes (PSNTs) that combine the novel features of fullerene and carbon nanotubes (CNTs), we study the thermal conductivity of a PSNT (1dp08) and its response to different strains by using non-equilibrium molecular dynamics simulations and lattice dynamics together with density functional theory. We find that the thermal conductivity of the PSNT is reduced by more than 90% as compared to that of CNTs, and remains almost the same when different strains applied, exhibiting very different behaviors from that of CNTs, where the thermal conductivity decreases monotonically with the increase of strain. Through phonon mode calculations, we show that the reduced phonon group velocity, phonon lifetime and the vibrational mismatch are responsible for the low thermal conductivity of the PSNT, and the insensitive response of thermal conductivity to strain is due to the insensitivity of its phonon density of states and group velocity to strain. These features endow the PSNT with the potential applications in thermal devices, and add new features to one-dimensional carbon nanomaterials going beyond conventional CNTs.

Phonon Dynamics in Anisotropic Dilute CuAl1–xFexO2 Delafossite Alloys by a Weighted Dynamical Matrix Approach

Here we report a new versatile approach for the calculation of phonon modes which is applicable to anisotropic, dilute alloys with allowance for a large variety of alloying elements. This approach ...

Thermal expansion in insulating solids from first principles

In this Tutorial, we describe the use of the quasiharmonic approximation and first-principles density functional theory (DFT) to calculate and analyze the thermal expansion of insulating solids. We discuss the theory underlying the quasiharmonic approximation and demonstrate its practical use within two common frameworks for calculating thermal expansion: the Helmholtz free energy framework and the Grüneisen theory. Using the example of silicon, we provide a guide for predicting how the lattice parameter changes as a function of temperature using DFT, including the calculation of phonon modes and phonon density of states, elastic constants, and specific heat. We also describe the calculation and interpretation of Grüneisen parameters, as well as how they relate to coefficients of thermal expansion. The limitations of the quasiharmonic approximation are briefly touched on, as well as the comparison of theoretical results with experimental data. Finally, we use the example of ferroelectric PbTiO3 to illustrate how the methods used can be adapted to study anisotropic systems.

Theoretical prediction of a charge-transfer phase transition

Phase transition materials are attractive from the viewpoints of basic science as well as practical applications. For example, optical phase transition materials are used for optical recording media. If a phase transition in condensed matter could be predicted or designed prior to synthesizing, the development of phase transition materials will be accelerated. Herein we show a logical strategy for designing a phase transition accompanying a thermal hysteresis loop. Combining first-principles phonon mode calculations and statistical thermodynamic calculations considering cooperative interaction predicts a charge-transfer phase transition between the A–B and A+–B− phases. As an example, we demonstrate the charge-transfer phase transition on rubidium manganese hexacyanoferrate. The predicted phase transition temperature and the thermal hysteresis loop agree well with the experimental results. This approach will contribute to the rapid development of yet undiscovered phase transition materials.

Cesium ion detection by terahertz light

Recent developments in terahertz technologies provide new tools for analysis, inspection, and nondestructive sensing. If a heavy atom is encapsulated in a cage of a porous material, the atom should vibrate slowly and resonate with a low-frequency terahertz light. From this perspective, a cyanide-bridged metal framework is a suitable system because it contains many cages that can adsorb Cs ions. Herein we show the vibration mode of a Cs ion in a cage of a cyanide-bridged metal framework. First-principles phonon mode calculations and terahertz time-domain spectroscopy (THz-TDS) measurements indicate that the vibration mode of a Cs ion in a cyanide-bridged manganese-iron framework is at 1.5 THz, which is significantly apart from other lattice vibrations. Taking advantage of this feature, we develop a THz-light detection method for Cs ions, which is useful for non-contact sensing of Cs ions in dangerous environments or harmful circumstances.

Anisotropy, phonon modes, and lattice anharmonicity from dielectric function tensor analysis of monoclinic cadmium tungstate

We determine the frequency dependence of four independent CdWO$_4$ Cartesian dielectric function tensor elements by generalized spectroscopic ellipsometry within mid-infrared and far-infrared spectral regions. Single crystal surfaces cut under different angles from a bulk crystal, (010) and (001), are investigated. From the spectral dependencies of the dielectric function tensor and its inverse we determine all long wavelength active transverse and longitudinal optic phonon modes with $A_u$ and $B_u$ symmetry as well as their eigenvectors within the monoclinic lattice. We thereby demonstrate that such information can be obtained completely without physical model line shape analysis in materials with monoclinic symmetry. We then augment the effect of lattice anharmonicity onto our recently described dielectric function tensor model approach for materials with monoclinic and triclinic crystal symmetries [Phys. Rev. B, 125209 (2016)], and we obtain excellent match between all measured and modeled dielectric function tensor elements. All phonon mode frequency and broadening parameters are determined in our model approach. We also perform density functional theory phonon mode calculations, and we compare our results obtained from theory, from direct dielectric function tensor analysis, and from model lineshape analysis, and we find excellent agreement between all approaches. We also discuss and present static and above reststrahlen spectral range dielectric constants. Our data for CdWO$_4$ are in excellent agreement with a recently proposed generalization of the Lyddane-Sachs-Teller relation for materials with low crystal symmetry [Phys. Rev. Lett. 117, 215502 (2016)].

Structures and thermoelectric properties of double-filled (CaxCe1−x)Fe4Sb12 skutterudites

The structures and thermoelectric properties of the double-filled (CaxCe1−x)Fe4Sb12 series (x=0, 0.25, 0.5, 0.75, and 1) have been studied using a combined experimental and computational methods. Compounds of (CaxCe1−x)Fe4Sb12 were obtained only for x=0, 0.5, and 1. Composition with x=0.25 was found to be a mixture of x=0 and 0.5 compounds, and composition with x=0.75 was found to be a mixture of x=1 and 0.5 compounds, respectively. Our conclusions on phase formation are supported by density functional theory (DFT) calculations. In Ca0.5Ce0.5Fe4Sb12, Ca substitution in the Ce site of CeFe4Sb12 leads to high hole concentrations, resulting in stronger semimetal transport as compared to CeFe4Sb12. Ca0.5Ce0.5Fe4Sb12 yields a slightly higher ZT value than that of CeFe4Sb12, which is attributed to its lower lattice thermal conductivity. Phonon mode calculations adopting a three-particle bending model suggest that thermal conductivity is reduced upon Ca substitution because of an additional vibration mode which involves both Ca and Ce atoms.

Theoretical Predictions of Freestanding Honeycomb Sheets of Cadmium Chalcogenides

Two-dimensional (2D) nanocrystals of CdX (X = S, Se, Te) typically grown by colloidal synthesis are coated with organic ligands. Recent experimental work on ZnSe showed that the organic ligands can be removed at elevated temperature, giving a freestanding 2D sheet of ZnSe. In this theoretical work, freestanding single- to few-layer sheets of CdX, each possessing a pseudo honeycomb lattice, are considered by cutting along all possible lattice planes of the bulk zinc blende (ZB) and wurtzite (WZ) phases. Using density functional theory, we have systematically studied their geometric structures, energetics, and electronic properties. A strong surface distortion is found to occur for all of the layered sheets, and yet all of the pseudo honeycomb lattices are preserved, giving unique types of surface corrugations and different electronic properties. The energetics, in combination with phonon mode calculations and molecular dynamics simulations, indicate that the syntheses of these freestanding 2D sheets could ...

X-ray absorption Debye-Waller factors fromab initiomolecular dynamics

An ab initio equation of motion method is introduced to calculate the temperature-dependent mean-square vibrational amplitudes ${\ensuremath{\sigma}}^{2}$ which appear in the Debye-Waller factors in x-ray absorption, x-ray scattering, and related spectra. The approach avoids explicit calculations of phonon modes, and is based instead on calculations of the displacement-displacement time correlation function from ab initio density functional theory molecular dynamics simulations. The method also yields the vibrational density of states and thermal quantities such as the lattice free energy. Illustrations of the method are presented for a number of systems and compared with other methods and experiment.

Monolayer honeycomb structures of group-IV elements and III-V binary compounds: First-principles calculations

Using first-principles plane wave calculations, we investigate two dimensional honeycomb structure of Group IV elements and their binary compounds, as well as the compounds of Group III-V elements. Based on structure optimization and phonon mode calculations, we determine that 22 different honeycomb materials are stable and correspond to local minima on the Born-Oppenheimer surface. We also find that all the binary compounds containing one of the first row elements, B, C or N have planar stable structures. On the other hand, in the honeycomb structures of Si, Ge and other binary compounds the alternating atoms of hexagons are buckled, since the stability is maintained by puckering. For those honeycomb materials which were found stable, we calculated optimized structures, cohesive energies, phonon modes, electronic band structures, effective cation and anion charges, and some elastic constants. The band gaps calculated within Density Functional Theory using Local Density Approximation are corrected by GW0 method. Si and Ge in honeycomb structure are semimetal and have linear band crossing at the Fermi level which attributes massless Fermion character to charge carriers as in graphene. However, all binary compounds are found to be semiconductor with band gaps depending on the constituent atoms. We present a method to reveal elastic constants of 2D honeycomb structures from the strain energy and calculate the Poisson's ratio as well as in-plane stiffness values. Preliminary results show that the nearly lattice matched heterostructures of ...