Studies of high-temperature electron–phonon interactions with inelastic neutron scattering and first-principles computations

Several recent studies of phonons combining inelastic neutron scattering and first-principles calculations are summarized. Inelastic neutron scattering was used to measure the phonon densities of states of the A15 compounds V₃Si, V₃Ge, and V₃Co at temperatures from 10 K to 1273 K. It was found that phonons in V₃Si and V₃Ge, which are superconducting at low temperatures, exhibit an anomalous stiffening with increasing temperature, whereas phonons in V₃Co have a normal softening behavior. Additional measurements of the phonon DOS of BCC V alloys were performed, and it was found that a stiffening anomaly present in pure V is suppressed upon introduction of extra d-electrons by alloying. First-principles calculations of the electronic and phonon densities of states show that in both these systems, the anomalous phonon stiffening originates with an adiabatic electron–phonon coupling mechanism. The anomaly is caused by the thermally-induced broadening of sharp peaks in the electronic density of states, which tends to decrease the electronic density at the Fermi level. These results illustrate how the combined use of first-principles calculations and inelastic neutron scattering provides powerful insights into couplings of excitations in condensed-matter.     

First-principle calculation for the phonon structure on iron-based superconductors

We perform first-principle phonon calculations for three typical iron-based superconductors, i.e., LaFeAsO,BaFe₂As₂, and FeSe. Though those crystals have different structures, we find that the optical modes associated with Fe vibration have almost similar characters. Moreover, we examine the pressure effect on phonons in FeSe. By increasing the external pressure, the phonon mode frequency related to Fe vibration effectively rises up and the electronic density of states at Fermi level also increases. These results may correlate to the critical temperature enhancement under high pressure.     

Vibronic Sidebands of Coherent Phonon States

Recently experiments have been reported about phonon sidebands in doped crystals, which may originate from coherent phonon states. The corresponding modes are either confined phonon modes in nanocrystals or localized phonon modes in bulk materials, both showing small damping due to phonon-phonon interaction. We present a theory of the lineshape of vibronic sideband spectra due to coherent phonon states using the conventional model of linear electron-phonon coupling and displaced equilibrium positions of the oscillators in the initial and final electronic states. Unlike in the conventional theory, the initial state of the oscillator is taken as a coherent phonon state and not as a thermalized one. Under these conditions we got an exact analytical solution for the lineshape of the vibronic sideband. The lineshape is determined by two parameters, the Huang-Rhys parameter S and the coherence parameter α of the phonon state. For α = 0 the lineshape converts into the standard Pekarian form for T = 0.     

First principles lattice dynamical calculation of semiboride Be2B and its ternary alloys XBeB (X=Na, Mg, Al)

We present results of first principles total energy calculations of the structure, electronic and lattice dynamics for beryllium semiboride and its three ternary alloys using generalized gradient and local density approximations under the framework of density functional theory. The generalized gradient approximation is used for all compounds except MgBeB using the Perdew-Burke-Ernzehorf exchange correlation functional while local density approximations use the Perdew-Zunger ultrasoft exchange correlation functional. The calculated ground state structural parameters are in good agreement with those of experimental and previous theoretical studies. The electronic band structure calculations show that Be₂B may transform to a semiconductor after Al substitution. A linear response approach to density functional theory is used to calculate phonon dispersion curves and vibrational density of states. The phonon dispersion curves of Be₂B and AlBeB are positive indicating a dynamical stablility of the structure for these compounds. The phonon dispersion curves of NaBeB and MgBeB show the imaginary phonons throughout the Brillouin zone, which confirms dynamical instability as indicated in band structures for these alloys. We also present the partial phonon density of states for different species of Be₂B and AlBeB to bring out the details of the participation of different atoms in the total phonon density of state, particularly the role played by Al atom. The first time calculated phonon properties are clearly able to bring out the significant effect of isoelectronic substitution in Be₂B.     

First principles study on the structural,electronic and phonon properties of monolayer B2Si

Using first principles density functional theory, we predict a monolayer B₂Si structure with space group Pmm2 in the present work. This structure is confirmed to be dynamically stable. Based on the plane wave pseudopotential approach, the charge density, electron localization function, density of states, energy band, phonon property and thermal conductivity of Pmm2-B₂Si are systematically studied. It is interesting that the sp² hybridization and coordination bond of Si are found in Pmm2-B₂Si, which is the most important factor for its structural stability. The density of states and energy band analysis reveals that Pmm2-B₂Si is metallic because of the partial occupied Si 3pz and B 2pz states. Moreover, the acoustic-optical coupling is important for phonon transport in Pmm2-B₂Si, and the contribution of optical modes to the lattice thermal conductivity along the [100] and [010] directions is 13% and 12%, respectively. This study gives a fundamental understanding of the structural, electronic and phonon properties in Pmm2-B₂Si.     

Dispersion and density of states of phonons and electrons in an α-B<Subscript>12</Subscript> crystal determined from first principles

Using the DFT method, we study the phonon properties of an α-B₁₂ rhombohedral crystal in the basis set of plane waves and its electronic structure in the localized basis set of Gaussians. It follows from the phonon dispersion that the crystal possesses a dynamical stability. The effective Born charges, the oscillator strengths, the transverse–longitudinal splitting, and the dielectric functions of dipole modes are calculated. We show that charge transfer from polar to equatorial atoms takes place in a В₁₂ icosahedron, while В–В bonds have predominantly a covalent character. In the density of states of acoustic modes, we reveal a structure that can manifest itself in the spectra of disordered boron compounds. From the dispersion of electronic bands, the occurrence of an indirect energy gap follows. The overlap of partial densities implies the hybridization of s and p electronic states in boron atoms.     

Raman spectra of cadmium titanate

Polarized Raman spectra of CdTiO₃ single crystals are recorded for the first time over the frequency range 5 < ν < 1000 cm^?1 at temperatures of 10 to 1200 K. The emphasis was on the low-frequency range, where an anomalous temperature dependence of a few phonon modes was observed. At high temperatures, four phonon modes exhibiting a behavior typical of soft modes were found to exist. These phonon modes are assumed to restore the cubic symmetry of the lattice. Their extrapolated temperature dependences suggest that there exists a sequence of three hypothetical high-temperature phase transitions analogous to those observed in the genuine perovskite CaTiO₃. At temperatures below 78 K, the Raman spectrum exhibits new lines associated with polar distortions of the unit cell. At low frequencies, three lines are observed whose parameters exhibit an anomalous behavior typical of soft modes in a ferroelectric phase. Several different polar states are assumed to exist at low temperatures.     

Phonons in mixed valence systems

The effect of valence changes due to f?d electronic transitions on phonons is studied. A large electronic density of states at the Fermi-energy in the intermediate valence state causes significant softening of the longitudinal acoustic and optic phonons and large phonon line-widths. These phonon renormalizations due to strong electron-lattice coupling are largest for phonon wavevectors q along the (111)-direction and maximal at the zone-boundary for LO modes and nearly half-way towards the zone-boundary in the case of LA mode. The results agree well with recent neutron scattering data on Sm_0.75Y_0.25S.     

Physical properties of the cubic spinel LiMn2O4

We have performed an ab initio study of structural, electronic, magnetic, vibrational and thermal properties of the cubic spinel LiMn₂O₄ by employing the density functional theory, the linear-response formalism, and the plane-wave pseudopotential method. An analysis of the electronic structure with the help of electronic density of states shows that the density of states at the Fermi level (N (E_F)) is found to be governed by the Mn 3d electrons with some contributions from the 2p states of O atoms. It is important to note that the contribution of Mn 3d states to N(_EF)$N\left(E_F\right)$ is as much as 85%. From our phonon calculations, we have obtained that the main contribution to phonon density of states (below 250 cm⁻¹) comes from the coupled motion of Mn and O atoms while phonon modes between 250 cm⁻¹ and 375 cm⁻¹ are characterized by the vibrations of all the three types of atoms. The contribution from Li increases rapidly at higher frequency (above 375 cm⁻¹) due to the light mass of this atom. Finally, the specific heat and the Debye temperature at 300 K are calculated to be 249.29 J/mol K and 820.80 K respectively.     

High pressure X-ray diffraction studies on UAI2, UAI2, and UAI4 systems

Abstract

The UAI₂, UAI₂, AND UAI₄ compounds have been studied by high pressure X-ray diffraction up to a maximum pressure of ～ 35 GPa. The compressibility behaviour of UAI₂ has been found to be consistent with the itinerant 5f states, whereas that of UAI₂ and UAI₄, indicate a more localized nature. Further, UAI₂ has been found to undergo a structural transition at ～ 11 GPa and the structure of the high pressure phase has been identified to be of MgNi₂ type with space group P6₃/mmc. The structure of UAI₂ at ambient pressure is of MgCu₂ type with space group Fd3m. From the electronic considerations, for instance, free electrons per atom ratio e/a, it is anticipated that it may transform back to MgCu₂ type structure at still higher pressures. On similar considerations, it is expected that most of the AB₂ type Laves phase compounds of the ‘f’ electron systems may undergo the structural sequence: MgCu₂ – MgZn₂ (or MgNi₂) – MgCu₂ due to increased delocalization of their ‘f’ electron states.     

Effect of hydrogen on the electronic properties of the superconducting metallic glass Zr2Pd

The effect of hydrogen on the electronic properties is studied for the superconducting metallic glass Zr₂Pd. Measurements of the mass density, electrical resistivity, thermoelectric power, the superconducting transition temperatureT _c and the upper critical field of Zr₂Pd with different hydrogen to metal ratios are given. Although the electronic density of states decreases steadily with increasing hydrogen content,T _c is constant forH/M values higher than 0.5. All results can be interpreted with two different binding states of the hydrogen for low and high hydrogen concentrations.Dedicated to B. Mühlschlegel on the occasion of his 60th birthday     

Inelastic neutron scattering and lattice dynamics of NaNbO<Subscript>3</Subscript> and Sr<Subscript>0.70</Subscript>Ca<Subscript>0.30</Subscript>TiO<Subscript>3</Subscript>

NaNbO₃ and (Sr,Ca)TiO₃ exhibit an unusual complex sequence of temperature- and pressure-driven structural phase transitions. We have carried out lattice dynamical studies to understand the phonon modes responsible for these phase transitions. Inelastic neutron scattering measurements using powder samples were carried out at the Dhruva reactor, which provide the phonon density of states. Lattice dynamical models have been developed for SrTiO₃ and CaTiO₃ which have been fruitfully employed to study the phonon spectra and vibrational properties of the solid solution (Sr,Ca)TiO₃.      

Raman study of phase transitions in rare earth vanadates

The phase transitions in DyVO₄ at about 14K and in TbVO₄ at about 33K have been investigated by Raman scattering. The E_g phonons are split below the transition temperature but the singlet phonon modes are not appreciably affected. No soft phonon mode is observed but large changes are seen in the low lying electronic levels. These results appear to be a consequence of a cooperative Jahn-Teller effect.     

Reply to the Comment on¶Low temperature specific heat of blue bronze K0.30MoO3

Eur. Phys. J. B 24, 315 (2001) In our Reply to the Comment [#!1!#] we refute the “straightforward” interpretation of the excess low-temperature specific heat, C_p, contribution we have measured in our study of CDW systems K_0.3MoO₃ and (TaSe₄)₂I [#!2!#] as originating solely from normal phonon modes. The specific sensitivity of the bump in C _p / T ³ at low temperatures to the impurity content is consistent with the increased value of the phason pinning gap while the dispersion of normal phonons remains unaffected. We ascribe at least this part of the anomaly to the phason contribution. As stated in reference [3] that the phonon density of states extracted from neutron scattering measurements is the least reliable in this energy range (<0.5 meV), we conclude that C_p measurements are more accurate for detecting the phason contribution. Received 17 April 2002 Published online 19 July 2002     

Raman spectral probe on increased local vibrational modes and phonon lifetimes in Ho3+‐doped Bi2O3 micro‐rods

We report the appearance and enhancement in intensity of impurity related local vibrational modes in Bi₂O₃ : Ho micro‐rods along with normal modes. Pure and Ho‐doped Bi₂O₃ micro‐rods were synthesized by conventional co‐precipitation method at 60 °C. The structural and morphological studies were carried out using powder X‐ray diffraction technique and scanning electron microscopy, respectively. Raman spectroscopic studies reveal the existence of local phonon vibrational modes (LVM) due to the incorporation of Ho³⁺. Harmonic approximation method was employed to find the dopant‐related peak in the Raman spectra. Variation in full width at half maximum for LVM with increase in Ho³⁺ was also investigated. This increase in FWHM indicates the decrease in crystallinity of the doped samples. The phonon lifetime calculation carried out for each samples and the decrease in phonon lifetime with doping concentration make this material a potential candidate for optical and electronic applications. Copyright © 2016 John Wiley & Sons, Ltd.     

Hydrogen storage: Lattice dynamics of orthorhombic NaMgH3

In this work, we investigate the structural, dynamic and thermodynamic properties of NaMgH₃, devoted for hydrogen storage. Density functional theory using pseudopotential methods and generalized gradient approximation has been used. A good agreement between the calculated structural parameters and the experimental data was found. A linear-response approach for the density functional theory is used in order to derive the Born effective charge tensors, the dielectric permittivity tensors, the phonon frequencies at the center of the Brillouin zone, the phonon-dispersion curves and the corresponding density of states for NaMgH₃ material. The obtained phonon frequencies at the zone center (Γ point) for the Raman-active and infrared-active modes are analyzed. Thermodynamic functions using the phonon density of states are also calculated.     

Coherence and spike death induced by bounded noise and delayed feedback in an excitable system

The first-principles total energy calculations with the generalised gradient approximation and the plane-wave pseudopotential method have been employed to investigate the structural, electronic and dynamical properties of Li₂TiO₃ (lithium titanate). The atomic structure is fully relaxed, and the structural parameters are found to differ by less than 1% from the experimental data. The indirect band-gap with 3.49 eV is predicted from the band structure calculations of this compound. The calculated phonon frequencies at the ??-point for the Raman-active and the infrared-active modes are presented and assigned. The phonon dispersion curves are also calculated along high symmetry lines in the Brillouin zone (BZ). Furthermore, the thermodynamic functions have been worked out using the corresponding phonon density of states, and the results indicate that they are in good agreement with available experimental values.     

A study of electronic structure and lattice dynamics of CoSb3 skutterudite

The novel filled skutterudite materials have attracted much interest in recent years and experimental studies have revealed that electrical properties (electrical conductivity and Seebeck coefficient) in these materials are dominated by their electronic structure while the effective suppression of thermal conductivity is mainly determined by their lattice dynamics. To clarify the relationship between microstructure and properties in further, we report a systematic study of electronic structures and lattice dynamics of CoSb₃ in this paper using linearized augmented plane waves based on the density functional theory of first principles. By calculating band structure and partial density of states (PDOS), effects of electronic structures of CoSb₃ on electrical properties were investigated. Based on the calculated results of phonon dispersions and phonon density of states of CoSb₃, lattice dynamics of CoSb₃ (heat capacity, Debye temperature, mean free path and lattice thermal conductivity) are discussed in detail. The calculated results are excellently consistent with other work and experimental data.     

Electronic Structure,Mechanical and Dynamical Stability of Hexagonal Subcarbides M<Subscript>2</Subscript>C (M = Tc,Ru, Rh,Pd, Re,Os, Ir,and Pt): Ab Initio Calculations

Ab initio calculations were used to study the properties of a series of hexagonal (Fe₂N-like) subcarbides M₂C, where M = Tc, Ru, Rh, Pd, Re, Os, Ir, and Pt, and to calculate their equilibrium structural parameters, electronic properties, phase stability, elastic constants, compression modulus, shear modulus, Young’s modulus, compressibility, Pugh’s indicator, Poisson ratio, elastic anisotropy indices, and also hardness, Debye temperature, sound velocity, and low-temperature heat capacity. It is found based on these results that all the subcarbides are mechanically stable; however, their formation energies E_form are positive with respect to a mixture of d-metal and graphite. In addition, the calculation of the phonon spectra of these subcarbides shows the existence of negative modes, which indicates their dynamical instability. Thus, a successful synthesis of these subcarbides at normal conditions is highly improbable.     

Enhanced Fröhlich interaction of semiconductor cuprous oxide films determined by temperature‐dependent Raman scattering and spectral transmittance

Anomalous low temperature behaviors in cuprous oxide (Cu₂O) film grown on quartz substrate have been investigated by temperature‐dependent Raman and transmittance spectra. The longitudinal optical components of two Γ₁₅‐ phonon modes become sharper and more intense at a low temperature. It can be found that the highest‐order electronic transition located at 6.4 eV exhibits a minimum transmittance near 200 K. Correspondingly, the variations from phonon intensity ratios reveal obvious anomalies with the decreasing temperature, indicating the existence of strong electron–phonon coupling mediated by Fröhlich interaction in the Cu₂O films below the temperature of 200 K. Copyright © 2012 John Wiley & Sons, Ltd.