Ab Initio Lattice Dynamics Calculations Research Articles

Infrared and Raman Diagnostic Modeling of Phosphate Adsorption on Ceria Nanoparticles.

Cerium dioxide (CeO2; ceria) nanoparticles (CeNPs) are promising nanozymes that show a variety of biological activity. Effective nanozymes need to retain their activity in the face of surface speciation in biological environments, and characterizing surface speciation is therefore critical to understanding and controlling the therapeutic capabilities of CeNPs. In particular, adsorbed phosphates can impact the enzymatic activity exploited to convert phosphate prodrugs into therapeutics in vivo and also define the early stages of the phosphate-scavenging processes that lead to the transformation of active CeO2 into inactive CePO4. In this work, we utilize ab initio lattice-dynamics calculations to study the interaction of phosphates with the three major surfaces of ceria and to predict the infrared (IR) and Raman spectral signatures of adsorbed phosphate species. We find that phosphates adsorb strongly to CeO2 surfaces in a range of stable binding configurations, of which 5-fold coordinated P species in a trigonal bipyramidal coordination may represent a stable intermediate in the early stages of phosphate scavenging. We find that the phosphate species show characteristic spectral fingerprints between 500 and 1500 cm-1, whereas the bare CeO2 surfaces show no active modes above 600 cm-1, and the 5-fold coordinated P species in particular show potential diagnostic P-O stretching modes between 650 and 700 cm-1 in both IR and Raman spectra. This comprehensive exploration of different binding modes for phosphates on CeO2 and the set of reference spectra provides an important step toward the experimental characterization of phosphate speciation and, ultimately, control of its impact on the performance of ceria nanozymes.

Nanoarhitectonics of Inorganic-Organic Silica-Benzil Composites: Synthesis, Nanocrystal Morphology and Micro-Raman Analysis.

The synthesis of nanosized organic benzil (C6H5CO)2 crystals within the mesoporous SiO2 host matrix was investigated via X-ray diffraction, transmission electron microscopy, Raman spectroscopy, and ab initio lattice dynamics analysis. Combining these methods, we have proved that the main structural properties of benzil nanocrystals embedded into SiO2 host membranes with pore diameters of 6.0, 7.8, 9.4, and 13.0 nm are preserved compared to a bulk benzil crystal. Space confinement has an insignificant impact on the lattice vibrational properties of benzil crystals implanted into the host matrices. The ab initio lattice dynamics calculation of the phonon spectrum in the Brillouin zone center shows the mechanical and dynamical stability of benzil lattice, revealing very low optical frequency of 11 cm-1 at point Γ.

Combined inelastic neutron scattering and ab initio lattice dynamics study of FeSi

The phonon renormalization across the semiconductor-to-metal crossover in FeSi is investigated by inelastic neutron scattering combined with ab initio lattice dynamical calculations. A significant part of reciprocal space with a particular focus on the $110\ensuremath{-}001$ scattering plane is mapped by the time-of-flight inelastic neutron scattering data taken below and above the crossover. Individual momentum values are investigated in more detail as a function of temperature. The data reveal that the anomalous phonon softening upon metallization is not exclusive to the high symmetry $R$ and $\mathrm{\ensuremath{\Gamma}}$ points. Several other phonon modes around the $R$ point as well as the phonon modes at the $M$ and $X$ points of the Brillouin zone exhibit anomalous phonon softening with magnitudes comparable to that observed at the $R$ point. The momentum dependence of the phonon softening is reproduced by the lattice dynamical calculation based on the density functional perturbation theory. We discuss our findings with respect to the nature of the semiconductor-to-metal crossover in FeSi, for which different microscopic origins have been proposed, i.e., lattice thermal disorder and electronic correlation effects.

On the issue of textured crystallization of Ba(NO3)2 in mesoporous SiO2: Raman spectroscopy and lattice dynamics analysis

The lattice dynamics of preferentially aligned nanocrystals formed upon drying of aqueous Ba(NO3)2 solutions in a mesoporous silica glass traversed by tubular pores of approximately 12 nm are explored by Raman scattering. To interpret the experiments on the confined nanocrystals polarized Raman spectra of bulk single crystals and X-ray diffraction experiments are also performed. Since a cubic symmetry is inherent to Ba(NO3)2, a special Raman scattering geometry was utilized to separate the phonon modes of Ag and Eg species. Combining group-theory analysis and ab initio lattice dynamics calculations a full interpretation of all Raman lines of the bulk single crystal is achieved. Apart from a small confinement-induced line broadening, the peak positions and normalized peak intensities of the Raman spectra of the nanoconfined and macroscopic crystals are identical. Interestingly, the Raman scattering experiment indicates the existence of comparatively large,∼10–20 μm, single-crystalline regions of Ba(NO3)2 embedded in the porous host, near three orders of magnitude larger than the average size of single nanopores. This is contrast to the initial assumption of non-interconnected pores. It rather indicates an inter-pore propagation of the crystallization front, presumably via microporosity in the pore walls.

Absence of temperature-dependent phonon anomalies in Sr2IrO4 and Sr3Ir2O7

Following previous works reporting an anomalous behavior of several zone-center optical phonons across the magnetic transition of square lattice iridates ${\mathrm{Sr}}_{2}{\mathrm{IrO}}_{4}$ and ${\mathrm{Sr}}_{3}{\mathrm{Ir}}_{2}{\mathrm{O}}_{7}$, we have investigated the lattice dynamics as a function of momentum in these materials by means of high-resolution inelastic x-ray scattering. The observed phonon energies and scattering intensities across the Brillouin zone are in excellent agreement with ab initio lattice dynamical calculations based on nonmagnetic density-functional-perturbation theory. Our results do not evidence any renormalization of the phonons at finite momentum across the magnetic transition of ${\mathrm{Sr}}_{2}{\mathrm{IrO}}_{4}$. The only anomalous behavior was detected for the in-plane polarized longitudinal-acoustic phonon branch in ${\mathrm{Sr}}_{3}{\mathrm{Ir}}_{2}{\mathrm{O}}_{7}$, which anomalously softens towards low temperatures and might be related to anisotropic negative thermal expansion in this compound. No anomalies related to potential charge ordering were observed.

Anomalous transverse optical phonons in SnTe and PbTe

We present a study of the soft transverse optic phonon mode in SnTe in comparison to the corresponding mode in PbTe using inelastic neutron scattering and ab-initio lattice dynamical calculations. In contrast to previous reports our calculations predict that the soft mode in SnTe features a strongly asymmetric spectral weight distribution qualitatively similar to that found in PbTe. Experimentally, we find that the overall width in energy of the phonon peaks is comparable in our neutron scattering spectra for SnTe and PbTe. We observe the well-known double-peak-like signature of the TO mode in PbTe even down to $T$ = 5 K questioning its proposed origin purely based on phonon-phonon scattering. The proximity to the incipient ferroelectric transition in PbTe likely plays an important role not included in current models.

Electron-momentum dependence of electron-phonon coupling underlies dramatic phonon renormalization in YNi2B2C

Electron-phonon coupling, i.e., the scattering of lattice vibrations by electrons and vice versa, is ubiquitous in solids and can lead to emergent ground states such as superconductivity and charge-density wave order. A broad spectral phonon line shape is often interpreted as a marker of strong electron-phonon coupling associated with Fermi surface nesting, i.e., parallel sections of the Fermi surface connected by the phonon momentum. Alternatively broad phonons are known to arise from strong atomic lattice anharmonicity. Here, we show that strong phonon broadening can occur in the absence of both Fermi surface nesting and lattice anharmonicity, if electron-phonon coupling is strongly enhanced for specific values of electron-momentum, k. We use inelastic neutron scattering, soft x-ray angle-resolved photoemission spectroscopy measurements and ab-initio lattice dynamical and electronic band structure calculations to demonstrate this scenario in the highly anisotropic tetragonal electron-phonon superconductor YNi2B2C. This new scenario likely applies to a wide range of compounds.

Origin of Ferroelectricity in Two Prototypical Hybrid Organic-Inorganic Perovskites.

Hybrid organic-inorganic perovskite (HOIP) ferroelectrics are attracting considerable interest because of their high performance, ease of synthesis, and lightweight. However, the intrinsic thermodynamic origins of their ferroelectric transitions remain insufficiently understood. Here, we identify the nature of the ferroelectric phase transitions in displacive [(CH3)2NH2][Mn(N3)3] and order-disorder type [(CH3)2NH2][Mn(HCOO)3] via spatially resolved structural analysis and ab initio lattice dynamics calculations. Our results demonstrate that the vibrational entropy change of the extended perovskite lattice drives the ferroelectric transition in the former and also contributes importantly to that of the latter along with the rotational entropy change of the A-site. This finding not only reveals the delicate atomic dynamics in ferroelectric HOIPs but also highlights that both the local and extended fluctuation of the hybrid perovskite lattice can be manipulated for creating ferroelectricity by taking advantages of their abundant atomic, electronic, and phononic degrees of freedom.

Heat transport through propagon-phonon interaction in epitaxial amorphous-crystalline multilayers

Managing heat dissipation is a necessity for nanoscale electronic devices with high-density interfaces, but despite considerable effort, it has been difficult to establish the phonon transport physics at the interface due to a “complex” interface layer. In contrast, the amorphous/epitaxial interface is expected to have almost no “complex” interface layer due to the lack of lattice mismatch strain and less associated defects. Here, we experimentally observe the extremely-small interface thermal resistance per unit area at the interface of the amorphous-germanium sulfide/epitaxial-lead telluride superlattice (~0.8 ± 4.0 × 10‒9 m2KW−1). Ab initio lattice dynamics calculations demonstrate that high phonon transmission through this interface can be predicted, like electron transport physics, from large vibron-phonon density-of-states overlapping and phonon group velocity similarity between propagon in amorphous layer and “conventional” phonon in crystal. This indicates that controlling phonon (or vibron) density-of-states and phonon group velocity similarity can be a comprehensive guideline to manage heat conduction in nanoscale systems.

Colloidal Cu2ZnSnS4-based and Ag-doped Nanocrystals: Synthesis and Raman Spectroscopy Study

Cu2ZnSnS4 (CZTS) is one of the promising materials for absorber layers of new-generation thin film solar cells. Various synthetic routes of materials preparation and structural characterization have been explored so far. Further tuning of the CZTS properties is realized via partial substitution of the cations. Here we have used an affordable and scalable method of synthesizing colloidal CZTS nanocrystals (NC) in an aqueous solution. Variation of the synthesis parameters, in particular pH of the solution, was employed to improve the crystallinity of the NCs. Furthermore, CZTS NCs with partial substitution of Cu for Ag were also successfully synthesized. Raman spectroscopy was employed as a prime tool of structural characterization of the NCs obtained, along with optical absorption spectroscopy and ab initio DFT lattice dynamics calculations. An experimentally observed slight upward shift of the main phonon Raman peak upon increase of the Ag content in (AgxCu1-x)2ZnSnS4 NCs is in agreement with the trend predicted by DFT calculation. No pure Ag2ZnSnS4 NCs could be formed, indicating a critical role of Cu in forming the kesterite structure NCs under given synthesis conditions in an aqueous medium.

Melting curve of vanadium up to 256 GPa: Consistency between experiments and theory

The melting curve of vanadium at high pressure and temperature (P-T) is of great interest to our understanding of $d$-orbital transition metals with simple crystal structures at extreme P-T conditions. Here we have investigated the melting curve and crystal structures of polycrystalline vanadium at high P-T using synchrotron x-ray diffraction (XRD) in laser-heated diamond anvil cells (LH DACs) up to \ensuremath{\sim}100 GPa and \ensuremath{\sim}4400 K, a two-stage light-gas gun with in situ shock temperature measurements up to \ensuremath{\sim}256 GPa and \ensuremath{\sim}6200 K, and ab initio molecular dynamics (AIMD) with density functional theory computations up to \ensuremath{\sim}200 GPa. The occurrence of the diffuse scattering signals in high P-T XRD patterns is used as the primary criterion to determine the melting curve of body-centered cubic (bcc) vanadium up to \ensuremath{\sim}100 GPa in LH DACs. Analysis of thermal radiation spectra of shocked vanadium using a quasispectral pyrometer constrains the melting curve up to \ensuremath{\sim}246 GPa and \ensuremath{\sim}5830 K, which is consistent with our static results using the Simon equation. The present static and dynamic experiments on the melting curve of vanadium are consistent with our AIMD simulations with the two-phase melting modeling, and are overall consistent with other theoretical simulations using the Z method. The results reconcile the recently reported theoretical discrepancy, and refute a higher melting curve report given by self-consistent ab initio lattice dynamics calculations. The consistencies among our studies indicate that one does not have to invoke superheating as a hypothesis to describe the solid-liquid equilibrium boundary of vanadium as an explanation for static vs dynamic experimental results. Our static and dynamic results with in situ diagnostics of melting and two-phase AIMD simulation have implications for studying melting curves of other $d$-orbital transition metals and their alloys at extreme P-T conditions.

Spin–phonon coupling and thermodynamic behaviour in YCrO3 and LaCrO3: inelastic neutron scattering and lattice dynamics

We report detailed temperature-dependent inelastic neutron scattering and ab initio lattice dynamics investigation of magnetic perovskites YCrO3 and LaCrO3. The magnetic neutron scattering from the Cr ions exhibits significant changes with temperature and dominates at low momentum transfer regime. Ab initio calculations performed including magnetic interactions show that the effect of magnetic interactions is very significant on the low- as well as high-energy phonon modes. We have also shown that the inelastic neutron spectrum of YCrO3 mimics the magnon spectrum from a G-type antiferromagnetic system, which is consistent with previously reported magnetic structure in the compound. The pressure-dependent ab initio lattice dynamics calculations are used to calculate the anisotropic thermal expansion behaviour in orthorhombic YCrO3, which is in excellent agreement with the available experimental data in the paramagnetic phase. We identify that the low energy anharmonic phonon modes involving Y vibrations contribute maximum to the thermal expansion behaviour.

Vibrational dynamics of the type-I clathrates A8Sn44□2 (A = Cs, Rb, K) from lattice-dynamics calculations, inelastic neutron scattering, and specific heat measurements

We report on a joint theoretical and experimental study of the vibrational dynamics of the type-I clathrates A8Sn44□2 (A = K, Rb, Cs, and □ stands for a vacancy) by high-resolution inelastic neutron scattering experiments combined with low-temperature specific heat measurements (2–300 K). Ab initio lattice dynamics calculations were performed on hypothetical vacancy-free A8Sn46 clathrates in order to determine the phonon dispersions and vibrational density of states Z(ω). The temperature dependence of the generalized vibrational density of states (GVDOS) was traced from 420 K down to 50 K, paying particular attention to the low-energy region of the GVDOS spectra. In the Cs and Rb compounds, the inelastic signal at low energies is dominated by several peaks mainly associated with the dynamics of the alkali metal atoms A in the polyhedral cages of the clathrate structure. In contrast, the low-energy spectrum of the K compound features a more pronounced contribution of the weighed modes of the framework Sn atoms. Upon cooling, the A-weighted modes soften regardless of the nature of the alkali element. The shift observed is similar for the three compounds and of small amplitude, suggestive of a dominant quasi-harmonic behavior above 50 K. The distinct dynamics of the K atoms in comparison to Cs and Rb is further demonstrated by the analyses of the low-temperature specific heat data, indicating that the low-energy Sn-weighted modes cannot be described by a Debye model with Einstein-like contributions.

A combined deep inelastic neutron scattering and ab initio lattice dynamics study of the hydride anion dynamics and bonding in La2LiHO3 oxyhydride

Kobayashi et al (6279) (Science 2016, 351) reported recently the existence of pure H- conductivity in the oxyhydride La2−x−ySrx+yLiH1−x+yO3−y, while demonstrating its functionality through a prototype solid-state Ti/La2LiHO3/TiH2 battery. In this study, we probe the atomistic motion of La2LiHO3 obtained by the promising halide salt flux method, via a combination of deep inelastic neutron scattering (DINS) and ab initio lattice dynamics (LD) calculations verified by vibrational inelastic neutron spectroscopy (INS). We successfully describe the measured momentum distributions from DINS via our LD calculations, without observing any diffusion activation over the temperature range reported by Kobayashi et al. This observation is corroborated by model predictions from our LD study, which reveals that the hydride anions remain bound within a 3D-harmonic potential. We conclude that with the current synthesis parameters, the method produces a vacancy free lattice, and that a necessary ingredient for diffusive motion of H- is the presence of a large population of vacancies. Based on the harmonic prediction for the hydrogen kinetic energy, we derive a picture of the evolution of the effective bonding potential for the hydride anions, and link this to the dynamics associated with decomposition of the oxyhydride.

Lattice dynamics and negative thermal expansion in the framework compound ZnNi(CN)4 with two-dimensional and three-dimensional local environments

ZnNi(CN)$_4$ is a 3D framework material consisting of two interpenetrating PtS-type networks in which tetrahedral [ZnN$_4$] units are linked by square-planar [NiC$_4$] units. Both the parent compounds, cubic Zn(CN)$_2$ and layered Ni(CN)$_2$, are known to exhibit 3D and 2D negative thermal expansion (NTE), respectively. Temperature-dependent inelastic neutron scattering measurements were performed on a powdered sample of ZnNi(CN)$_4$ to probe phonon dynamics. The measurements were underpinned by ab initio lattice dynamical calculations. Good agreement was found between the measured and calculated generalized phonon density-of-states, validating our theoretical model and indicating that it is a good representation of the dynamics of the structural units. The calculated linear thermal expansion coefficients are $\alpha_a$=-21.2 $\times$ 10$^{-6}$ K$^{-1}$ and $\alpha_c$=+14.6$\times$10$^{-6}$K$^{-1}$, leading to an overall volume expansion coefficient $\alpha_V$ of -26.95$\times$10$^{-6}$K$^{-1}$, pointing towards pronounced NTE behavior. Analysis of the derived mode-Gr\"uneisen parameters shows that optic modes around 12 and 40 meV make a significant contribution to NTE. These modes involve localized rotational motions of the [NiC$_4$] and/or [ZnN$_4$] rigid units, echoing what has previously been observed in Zn(CN)$_2$ and Ni(CN)$_2$. However, in ZnNi(CN)$_4$, modes below 10 meV have the most negative Gr\"uneisen parameters. Analysis of their eigenvectors reveals that a large transverse motion of the Ni atom in the direction perpendicular to its square-planar environment induces a distortion of the units. This mode is a consequence of the Ni atom being constrained only in 2D within a 3D framework. Hence, although rigid-unit modes account for some of the NTE-driving phonons, the added d-o-f compared with Zn(CN)$_2$ results in modes with twisting motions, capable of inducing greater NTE.

Anomalous Lattice Dynamics in AgC4N3: Insights From Inelastic Neutron Scattering and Density Functional Calculations.

We have performed temperature dependent inelastic neutron scattering measurements to study the anharmonicity of phonon spectra of AgC4N3. The analysis and interpretation of the experimental spectra is done using ab-initio lattice dynamics calculations. The calculated phonon spectrum over the entire Brillouin zone is used to derive linear thermal expansion coefficients. The effect of van der Waals interaction on structure stability has been investigated using advanced density functional methods. The calculated isothermal equation of states implies a negative linear compressibility along the c-axis of the crystal, which also leads to a negative thermal expansion along this direction. The role of elastic properties inducing the observed anomalous lattice behavior is discussed.

An Unusual Phase Transition Driven by Vibrational Entropy Changes in a Hybrid Organic–Inorganic Perovskite

The driving forces for the phase transitions of ABX3 hybrid organic-inorganic perovskites have been limited to the octahedral tilting, order-disorder, and displacement. Now, a complex structural phase transition has been explored in a HOIP, [CH3 NH3 ][Mn(N3 )3 ], based on structural characterizations and ab initio lattice dynamics calculations. This unusual first-order phase transition between two ordered phases at about 265 K is primarily driven by changes in the collective atomic vibrations of the whole lattice, along with concurrent molecular displacements and an unusual octahedral tilting. A significant entropy difference (4.35 J K-1 mol-1 ) is observed between the low- and high-temperature structures induced by such atomic vibrations, which plays a main role in driving the transition. This finding offers an alternative pathway for designing new ferroic phase transitions and related physical properties in HOIPs and other hybrid crystals.

An Unusual Phase Transition Driven by Vibrational Entropy Changes in a Hybrid Organic–Inorganic Perovskite

AbstractThe driving forces for the phase transitions of ABX3 hybrid organic–inorganic perovskites have been limited to the octahedral tilting, order–disorder, and displacement. Now, a complex structural phase transition has been explored in a HOIP, [CH3NH3][Mn(N3)3], based on structural characterizations and ab initio lattice dynamics calculations. This unusual first‐order phase transition between two ordered phases at about 265 K is primarily driven by changes in the collective atomic vibrations of the whole lattice, along with concurrent molecular displacements and an unusual octahedral tilting. A significant entropy difference (4.35 J K−1 mol−1) is observed between the low‐ and high‐temperature structures induced by such atomic vibrations, which plays a main role in driving the transition. This finding offers an alternative pathway for designing new ferroic phase transitions and related physical properties in HOIPs and other hybrid crystals.

Lattice dynamics of ASb2O6 ( A=Cu , Co) with trirutile structure

Raman spectroscopy experiments on single crystals of CuSb2O6 and CoSb2O6 quasi-one-dimensional antiferromagnets with trirutile crystal structure were performed, with a focus on the first material. The observed Raman-active phonon modes and previously reported infrared-active modes were identified with the aid of ab-initio lattice dynamics calculations. The structural transition between monoclinic beta-CuSb2O6 and tetragonal alpha-CuSb2O6 phases at Ts=400 K is manifested in our spectra by a "repulsion" of two accidentally quasi-degenerate symmetric modes below Ts, caused by a phonon mixing effect that is only operative in the monoclinic beta-CuSb2O6 phase due to symmetry restrictions. Also, two specific phonons, associated with CuO6 octahedra rotation and with a Jahn-Teller elongation mode, soften and broaden appreciably as T -> Ts. A crossover from a displacive to an order-disorder transition at Ts is inferred.

Lattice Thermal Conductivity of MgSiO3 Perovskite from First Principles

We investigate lattice thermal conductivity κ of MgSiO3 perovskite (pv) by ab initio lattice dynamics calculations combined with exact solution of linearized phonon Boltzmann equation. At room temperature, κ of pristine MgSiO3 pv is found to be 10.7 W/(m · K) at 0 GPa. It increases linearly with pressure and reaches 59.2 W/(m · K) at 100 GPa. These values are close to multi-anvil press measurements whereas about twice as large as those from diamond anvil cell experiments. The increase of k with pressure is attributed to the squeeze of weighted phase-spaces phonons get emitted or absorbed. Moreover, we find κ exhibits noticeable anisotropy, with κzz being the largest component and ({{boldsymbol{kappa }}}_{{rm{max }}}-{{boldsymbol{kappa }}}_{{rm{min }}})/bar{{boldsymbol{kappa }}} being about 25%. Such extent of anisotropy is comparable to those of upper mantle minerals such as olivine and enstatite. By analyzing phonon mean free paths and lifetimes, we further show that the weak temperature dependence of κ observed in experiments should not be caused by phonons reaching ‘minimum’ mean free paths. These results clarify the microscopic mechanism of thermal transport in MgSiO3 pv, and provide reference data for understanding heat conduction in the Earth’s deep interior.