Vibrational Density Of States Research Articles

Machine learning potentials of kaolinite based on the potential energy surfaces of GGA and meta-GGA density functional theory

Machine learning molecular dynamics (MLMD) is a promising method for predicting material properties with high accuracy and low computational costs. Two kaolinite machine learning potentials (MLPs) were created based on a dataset that consists of the results of the first-principles calculations with the Perdew–Burke–Ernzerhof (PBE) generalized gradient approximation (GGA) and the strongly constrained and appropriately normed (SCAN) mata-GGA functionals. The structural and mechanical properties of kaolinite were evaluated by the MLMD simulations with the MLPs. The results were compared with those obtained by the density functional theory simulations, classical molecular dynamics simulations, and experiments. The MLMD with the MLP based on SCAN performed well for an accurate evaluation of these kaolinite properties. The vibrational density of states of kaolinite was evaluated using the MLPs, and the results were compared with inelastic neutron scattering experiment data. The MLP based on SCAN agreed well with the experimental results. Remarkably, the MLP successfully reproduced the spectral shape in the low-wavenumber, where evaluation requires a long-time simulation with high accuracy.

Tuning Network Connectivity of Silicate and Sodium Borosilicate Glasses by TiO2 for Enhanced Chemical Durability: Molecular Dynamics Simulation Investigations.

Extensive molecular dynamics (MD) simulations were performed to disclose the beneficial aspects of TiO2 doping in SiO2 and sodium borosilicate (NBS) glasses. Significant amendment in short- and intermediate-range orders of glasses was captured by the radial distribution function, coordination number, bond/angle distribution profiles, structure factor, and probability of linking X-O-X' (where X and/or X' = Si, B, and Ti) structural motifs. Successively, the effect of microscopic structural modification on the macroscopic properties was analyzed in terms of mechanical strength, thermal stability, vibrational characteristics [(vibrational density of states (VDOS)], and chemical durability. The results show that Ti participates in the network chain in the form of TiO6 and TiO5 for the Ti-NBS glass whereas in the form of TiO6, TiO5, and TiO4 for the binary TiO2-SiO2 glass. The presence of TiO2 was found to strengthen the glass skeleton. However, the glass-transition temperature was also increased with Ti addition, which indicates increased hurdles during synthesis due to increased cross connections in the glass network with Ti doping. The computed results envisage enhanced chemical durability of Ti-added glasses. In addition, VDOS spectra showed network former-like characteristics of Ti in the glass network with significant contributions up to a vibration frequency of 800 cm-1. The strong binding of Ti-O-connected Na+ in the glass skeleton prevents Na+ migration toward the interface or bulk aqueous phase, which contributes to improved chemical stability of Ti-containing glasses. During contact with water, Na+ were less likely to leach out from glass to the aqueous solution during Ti doping. In addition, the increased fraction of stable ring structures (5m-7m) for Ti-NBS glasses than bare NBS glasses also supports the increased leaching resistivity of Ti-added glasses. Essentially, the elucidation of macroscopic glass properties has been provided in terms of microscopic understanding. The present findings will incite further MD simulations and experiments to disclose more interesting microstructures and dynamics due to the presence of TiO2 in glasses.

Thermodynamic properties of geikielite (MgTiO3) and ilmenite (FeTiO3) derived from vibrational methods combined with Raman and infrared spectroscopic data

We present a model for the lattice vibrational density of states of MgTiO3 (geikielite) and FeTiO3 (ilmenite) that predicts thermodynamic properties, in agreement with observational data. The model is based on Kieffer’s method combined with spectroscopic data. For both substances experimental data sets are influenced by non-stoichiometry. For geikielite that affects the volume, whereas for ilmenite volume and bulk modulus are affected. We show that Kieffer’s method enables predicting bulk moduli in pressure–temperature space. We demonstrate that intrinsic anharmonicity or electronic effects significantly affect the heat capacity of ilmenite, whereas that is not the case for geikielite. We use Kieffer’s method to derive multiple-Einstein models, from which we demonstrate that thermodynamic properties are insignificantly influenced by dispersion in Grüneisen, mode-q and anharmonicity parameters for both substances. We show that our results enable predicting thermodynamic properties and shear modulus of the solid solution formed from geikielite and ilmenite. Geikielite and ilmenite are added to our thermodynamic database for the system MgO–SiO2–FeO, to enable modeling phase stability and physical properties of titanium-rich reservoirs in the Earth’s Moon.

Role of Optical Phonons and Anharmonicity in the Appearance of the Heat Capacity Boson Peak-like Anomaly in Fully Ordered Molecular Crystals.

We demonstrate that the heat capacity Boson peak (BP)-like anomaly appearing in fully ordered anharmonic molecular crystals emerges as a result of the strong interactions between propagating (acoustic) and low-energy quasi-localized (optical) phonons. In particular, we experimentally determine the low-temperature (<30 K) specific heat of the molecular crystal benzophenone and those of several of its fully ordered bromine derivatives. Subsequently, by means of theoretical first-principles methods based on density functional theory, we estimate the corresponding phonon dispersions and vibrational density of states. Our results reveal two possible mechanisms for the emergence of the BP-like anomaly: (i) acoustic–optic phonon avoided crossing, which gives rise to a pseudo-van Hove singularity in the acoustic phonon branches, and (ii) piling up of low-frequency optical phonons, which are quasi degenerate with longitudinal acoustic modes and lead to a surge in the vibrational density of states at low energies.

Predicting plasticity of amorphous solids from instantaneous normal modes.

We present a mathematical description of amorphous solid deformation and plasticity by extending the concept of instantaneous normal modes (INMs) to deformed systems, which allows us to retain the effect of strain on the vibrational density of states (VDOS). Starting from the nonaffine lattice dynamics (NALD) description of elasticity and viscoelasticity of glasses, we formulate the linear response theory up to large deformations by considering the strain-dependent tangent modulus at finite values of shear strain. The (nonaffine) tangent shear modulus is computed from the VDOS of affinely strained configurations at varying strain values. The affine strain, found analytically on the static (undeformed) snapshot of the glass, leads to configurations that are rich with soft low-energy modes as well as unstable modes (negative eigenvalues) that are otherwise completely "washed out" and lost if one lets the system fully relax after strain. This procedure is consistent with the structure of NALD. The INM spectrum of deformed states allows for the analytical prediction of the stress-strain curve of a model glass. Good parameter-free quantitative agreement is shown between the prediction and simulations of athermal quasistatic shear of a coarse-grained polymer glass.

Thermal transport of monolayer amorphous carbon and boron nitride

Amorphous materials feature localization of electrons and phonons that alter the electronic, mechanical, thermal, and magnetic properties. Here, we report calculations of the in-plane thermal conductivities of monolayer amorphous carbon and monolayer amorphous boron nitride, by reverse nonequilibrium molecular dynamics simulations. We find that the thermal conductivities of both monolayer amorphous carbon (MAC) and monolayer amorphous boron nitride (ma-BN) are about two orders of magnitude smaller than their crystalline counterparts. Moreover, the ultralow thermal conductivities are independent of the temperature and strain due to their extremely short heat carrier mean free paths. The relation between the structure disorder and the reduction of the thermal conductivity is analyzed in terms of the vibrational density of states and the participation ratio. The ma-BN shows strong vibrational localization across the frequency range, while the MAC exhibits a unique extended G* diffuson mode due to its sp2 hybridization and the broken E2g symmetry. The irregular vibrational patterns are also analyzed. The present results may enable potential applications of MAC and ma-BN in thermal management.

Atomistic evidence of hydrodynamic heat transfer in nanowires

With wave-packet propagation simulations and heat flux estimation via molecular dynamics, we show that the heat flux radial distribution in silicon nanowires can be described by a mesoscopic model, the hydrodynamic heat equation. We observe Poiseuille like heat flux profile, that cannot be described by a simple kinetic model such as the Fuchs-Sondheimer model, in both pristine and core/shell nanowires. The addition of a shell does not change the shape of the radial heat flux distribution, but just modifies the maximum of the heat flux in the center of the nanowire. These results show that there is a heat flux depletion length for pristine or core shell nanowires, 1–2 nm away from the boundary of the crystalline part. The parameters of the mesoscopic model are discussed in terms of microscopic properties, including the phonon mean free path as function of frequency and the partial vibrational density of states in the different regions of the nanowire.

Graphene coated 3C-SiC with improved irradiation resistance and enhanced heat conduction property after collision cascade

Graphene/SiC nanocomposites are promising materials with excellent irradiation resistance. In this study, the structure of 3C-SiC coated with graphene layers is proposed to improve SiC's irradiation resistance. The atomistic mechanisms behind the irradiation resistance and irradiation's effect on the thermal conductance of the composite are investigated through molecular dynamics simulations. Results show that the graphene layers effectively enhanced the irradiation resistance of SiC in the composite with increased threshold displacement energy when irradiated with a carbon primary knock-on atom (PKA). Influence factors, i.e., graphene layer number, incident angle of the PKA, and temperature, of irradiation resistance are also studied by collision cascade simulations. In addition, the heat conduction of the composite is enhanced after the irradiation with the 1.5 keV carbon PKA. The resistance dominates the thermal transport at the graphene layers near the interface instead of the interface. The largest temperature drop occurs between the interface and the penultimate graphene layer, consistent with the significant mismatch of their vibrational density of states. After irradiation with the 1.5 keV carbon PKA, the thermal conductance of the graphene/SiC composites increases, and the interface thermal resistance decreases due to the formed bonds between the graphene layers. Overall, this work provides a fundamental understanding of the irradiation resistance and the thermal properties of the graphene/SiC composite.

Vibrational Entropy of Crystalline Solids from Covariance of Atomic Displacements.

The vibrational entropy of a solid at finite temperature is investigated from the perspective of information theory. Ab initio molecular dynamics (AIMD) simulations generate ensembles of atomic configurations at finite temperature from which we obtain the N-body distribution of atomic displacements, . We calculate the information-theoretic entropy from the expectation value of . At a first level of approximation, treating individual atomic displacements independently, our method may be applied using Debye–Waller B-factors, allowing diffraction experiments to obtain an upper bound on the thermodynamic entropy. At the next level of approximation we correct the overestimation through inclusion of displacement covariances. We apply this approach to elemental body-centered cubic sodium and face-centered cubic aluminum, showing good agreement with experimental values above the Debye temperatures of the metals. Below the Debye temperatures, we extract an effective vibrational density of states from eigenvalues of the covariance matrix, and then evaluate the entropy quantum mechanically, again yielding good agreement with experiment down to low temperatures. Our method readily generalizes to complex solids, as we demonstrate for a high entropy alloy. Further, our method applies in cases where the quasiharmonic approximation fails, as we demonstrate by calculating the HCP/BCC transition in Ti.

Mechanical and thermal characterizations of nanoporous two-dimensional boron nitride membranes

Hexagonal boron nitride (h-BN) is a promising 2D material due to its outstanding mechanical and thermal properties. In the present study, we use molecular dynamics simulations to investigate the influence of porosity and temperature on the mechanical characteristics of h-BN based on uniaxial and biaxial tensions. Meanwhile, the progression of the microstructure of h-BN up to fracture is studied in order to clarify its fractures mechanism during the tension process. Our results reveal that depending on the porosity and tensile direction, the phase transition occurs more or less. The strength, and Young's modulus of h-BN membranes reduce as increasing porosity. Due to the presence of the pores, the most substantial stresses will be centred around the pores site in the tensile test. Then the fracture starts on the pore edge and spreads preferentially along the zigzag direction of h-BN. Furthermore, fracture strain, strength, and Young's modulus decrease when the temperature rises. In addition, the non-equilibrium molecular dynamics (NEMD) simulations are performed to investigate the influence of various porosities and temperatures on the thermal conductivity of h-BN membranes. The results reveal that the thermal conductivity is greatly reduced by nanoporous. The higher the porosity, the lower the thermal conductivity. The vibration density of states of h-BN membranes is calculated; the result suggests that the defects might reduce the phonon mean free path because of the high collision of the phonons. These alterations represent the scattering influence of defects on phonons, which reduces phonon life and considerably lowers thermal conductivity. Moreover, the findings also proved that as temperature increases, the intrinsic thermal conductivity of h-BN decreases. The thermal conductivity and mechanical properties of the pristine h-BN thin film are interestingly equivalent in the zigzag and armchair orientations.

Radiative relaxation in isolated large carbon clusters: Vibrational emission versus recurrent fluorescence.

Recurrent fluorescence (RF) from isolated carbon clusters containing between 24 and 60 atoms is theoretically investigated as a function of internal energy, cluster size, and structural features. The vibrational relaxation kinetics and the associated IR emission spectra are determined by means of a Monte Carlo approach with vibrational density of states computed in the harmonic approximation. RF is generally found to be highly competitive with vibrational emission. The behaviors predicted for clusters of various sizes and archetypal structures indicate that the IR emission spectra are strongly influenced by RF, an energy gap law being obtained for the evolution of the RF rate constant depending on the electronic excitation state. The present results are relevant to the photophysics of the interstellar medium and could contribute to elucidating the carriers of the extended red emission bands and the continuum emission lying below the aromatic infrared bands believed to originate from mixed aromatic-aliphatic compounds.

Heat conduction in polymer chains: Effect of substrate on the thermal conductance.

In standard molecular junctions, a molecular structure is placed between and connected to metal leads. Understanding how mechanical tuning in such molecular junctions can change heat conductance has interesting applications in nanoscale energy transport. In this work, we use nonequilibrium molecular dynamics simulations to address the effect of stretching on the phononic contribution to the heat conduction of molecular junctions consisting of single long-chain alkanes and various metal leads, such as Ag, Au, Cu, Ni, and Pt. The thermal conductance of such junctions is found to be much smaller than the intrinsic thermal conductance of the polymer and significantly depends on the nature of metal leads as expressed by the metal-molecule coupling and metal vibrational density of states. This behavior is expected and reflects the mismatch of phonon spectra at the metal molecule interfaces. As a function of stretching, we find a behavior similar to what was observed earlier [M. Dinpajooh and A. Nitzan, J. Chem. Phys. 153, 164903 (2020)] for pure polymeric structures. At relatively short electrode distances, where the polyethylene chains are compressed, it is found that the thermal conductances of the molecular junctions remain almost constant as one stretches the polymer chains. At critical electrode distances, the thermal conductances start to increase, reaching the values of the fully extended molecular junctions. Similar behaviors are observed for junctions in which several long-chain alkanes are sandwiched between various metal leads. These findings indicate that this behavior under stretching is an intrinsic property of the polymer chain and not significantly associated with the interfacial structures.

Experimental Confirmation of the Universal Law for the Vibrational Density of States of Liquids.

An analytical model describing the vibrational density of states (VDOS) of liquids has long been elusive, owing to the complexities of liquid dynamics. Nevertheless, Zaccone and Baggioli have recently developed such a model which was proposed to be the universal law for the vibrational density of states of liquids. Distinct from the Debye law, g(ω) ∝ ω2, for solids, the universal law for liquids reveals a linear relationship, g(ω) ∝ ω, in the low-energy region. We have confirmed this universal law with experimental VDOS measured by inelastic neutron scattering on real liquid systems including water, liquid metal, and polymer liquids, and have applied this model to extract the effective relaxation rate for the short time dynamics for each liquid. The model has also been further evaluated in the prediction of the specific heat with comparison to existing experimental data as well as with values obtained by different approaches.

First-principles thermochemical properties of hexagonal and cubic phase BaMnO3

BaMnO3 perovskite oxide is an interesting material for many high-temperature technological applications due to its facile reduction capacity at reasonably low temperature. The thermochemical properties of BaMnO3 largely determine this reduction behaviour at high temperature. However, the temperature-dependent thermochemical properties of hexagonal and cubic BaMnO3 remain uncharacterized. Herein the structural and thermochemical properties (entropy, specific heat and relative molar enthalpy) of hexagonal and cubic BaMnO3 perovskites are predicted using first principles calculations. Their corresponding phonon dispersions and vibrational density of states are illustrated to show the individual atomic contributions to their thermochemical properties. It is demonstrated that the choice of generalized gradient approximation DFT functional does not appreciably influence the structural or thermochemical properties. Data AvailabilityThe raw data required to reproduce these findings are available from the authors upon reasonable request.

Near-Interface Defects in Graphene/H-BN In-Plane Heterostructures: Insights into the Interfacial Thermal Transport.

Based on nonequilibrium molecular dynamics (NEMD) and nonequilibrium Green’s function simulations, the interfacial thermal conductance (ITC) of graphene/h-BN in-plane heterostructures with near-interface defects (monovacancy defects, 585 and f5f7 double-vacancy defects) is studied. Compared to pristine graphene/h-BN, all near-interface defects reduce the ITC of graphene/h-BN. However, differences in defective structures and the wrinkles induced by the defects cause significant discrepancies in heat transfer for defective graphene/h-BN. The stronger phonon scattering and phonon localization caused by the wider cross-section in defects and the larger wrinkles result in the double-vacancy defects having stronger energy hindrance effects than the monovacancy defects. In addition, the approximate cross-sections and wrinkles induced by the 585 and f5f7 double-vacancy defects provide approximate heat hindrance capability. The phonon transmission and vibrational density of states (VDOS) further confirm the above results. The double-vacancy defects in the near-interface region have lower low-frequency phonon transmission and VDOS values than the monovacancy defects, while the 585 and f5f7 double-vacancy defects have similar low-frequency phonon transmission and VDOS values at the near-interface region. This study provides physical insight into the thermal transport mechanisms in graphene/h-BN in-plane heterostructures with near-interface defects and provides design guidelines for related devices.

Defect-Engineered Thermal Transport in Wrinkled Graphene: A Comprehensive Molecular Dynamics Study

The out-of-plane morphology of graphene can be easily engineered with topological defects so as to adjust its thermal and mechanical properties. Herein, the heat transport behaviors of graphene with topological defect-induced wrinkles are systematically investigated by using nonequilibrium molecular dynamics simulations. Distinct from pristine graphene, the wrinkled graphene exhibits much lower thermal conductivity. By analyzing the vibrational density of states and atomic heat flux distribution, it is found that the phonon scattering enhancement caused by topological defects is the major mechanism of the thermal conductivity decrease, especially for the wrinkled graphene with a large aspect ratio of wrinkles. Besides, the thermal conductivity of wrinkled graphene is insensitive to sample size due to the extremely low phonon mean free path (MFP) caused by the topological defects. Furthermore, the thermal conductivity of wrinkled graphene is also insensitive to temperature due to the low MFP as well as the large contribution of low-frequency phonons in thermal transport. The present study offers a physical insight into the mechanisms of topological defects on thermal transport of graphene, which may offer topological optimization strategies for engineering the thermal conductivity of graphene with defects.

Reversible motions and disordered structure of soft particles in amorphous solids

In amorphous solids, soft vibrational modes derived from normal mode analysis can be utilized to identify the soft particles that are prone to irreversible rearrangements. However, the normal mode analysis approach cannot explain why the spatial distributions of clustered soft particles do not change over time. We define a softness parameter based on the vibrational density of states calculated directly from molecular dynamics simulations with both the harmonic vibrations and anharmonic relaxations being properly captured at finite temperatures. This parameter spontaneously correlates with the real space atomic motions and the dynamics heterogeneity. Using the softness parameter, we show that the softest particles are confined within rigid cages. These particles keep rearranging reversibly without long-range diffusion. The moderately soft particles rearrange irreversibly, and the hard particles mainly participate in vibrations without rearrangement. We also show that the soft particles form locally disordered structures, while the hard particles present strong ordering. These findings confirm the defective nature of soft particles, and provide insights on the nature of softness as the ability to rearrange, but not necessarily irreversibly.

Localized Phonon Densities of States at Grain Boundaries in Silicon.

Since it is now possible to record vibrational spectra at nanometer scales in the electron microscope, it is of interest to explore whether extended defects in crystals such as dislocations or grain boundaries will result in measurable changes of the phonon densities of states (dos) that are reflected in the spectra. Phonon densities of states were calculated for a set of high angle grain boundaries in silicon. The boundaries are modeled by supercells with up to 160 atoms, and the vibrational densities of states were calculated by taking the Fourier transform of the velocity–velocity autocorrelation function from molecular dynamics simulations with larger supercells doubled in all three directions. In selected cases, the results were checked on the original supercells by comparison with the densities of states obtained by diagonalizing the dynamical matrix calculated using density functional theory. Near the core of the grain boundary, the height of the optic phonon peak in the dos at 60 meV was suppressed relative to features due to acoustic phonons that are largely unchanged relative to their bulk values. This can be attributed to the variation in the strength of bonds in grain boundary core regions where there is a range of bond lengths.

Vibrational properties of the mononuclear Fe[HBpz3]2 spin crossover complex

Within this work, we report the results of nuclear inelastic scattering experiments of the low-spin phase of the iron(II) mononuclear SCO complex Fe[HBpz3]2 and density functional theory based calculations performed on a model molecule of the complex. We show that the calculated partial density of vibrational states based on the structure of a single iron(II) center which is linked by three pyrazole rings to borat is in good accordance with the experimentally obtained 57Fe-pDOS and assign the molecular vibrations to the prominent optical phonons.

Raman spectroscopy of isotopically pure and diluted high‐ and low‐density amorphous ices

AbstractWe present an experimental and theoretical study of Raman spectroscopy of isotopically pure and diluted amorphous as well as crystalline ices at 30 K. Our experiments comprise polarized (VV) and depolarized (VH) spectra in the OH‐stretch region, whereas our calculations involve molecular dynamics (MD) simulation of the high‐ and low‐density amorphous ices through vitrification and subsequent formulation of vibrational Hamiltonian of coupled OH oscillators in the hydrogen‐bond network of the ices. Our theoretical Raman VV and VH spectra at each isotopic dilution are in good agreement with the experimental data. This allows us not only to carry out detailed spectral assignments for the amorphous and crystalline ices from the viewpoint of vibrational phase, delocalization, and density of states but also to confirm the reliability of the MD simulation in which deeply supercooled liquid water spontaneously separates into high‐ and low‐density fluid phases below a liquid–liquid critical point.