Vibrational Density Of States Research Articles

Superdiffusive Rotation of Interfacial Water on Noble Metal Surface.

Interfacial water on a metal surface acts as an active layer through the reorientation of water, thereby facilitating the energy transfer and chemical reaction across the metal surface in various physicochemical and industrial processes. However, how this active interfacial water collectively behaves on flat noble metal substrates remains largely unknown due to the experimental limitation in capturing librational vibrational motion of interfacial water and prohibitive computational costs at the first-principles level. Herein, by implementing a machine-learning approach to train neural network potentials, we enable performing advanced molecular dynamics simulations with ab initio accuracy at a nanosecond scale to map the distinct rotational motion of water molecules on a metal surface at room temperature. The vibrational density of states of the interfacial water with two-layer profiles reveals that the rotation and vibration of water within the strong adsorption layer on the metal surface behave as if the water molecules in the bulk ice, wherein the O-H stretching frequency is well consistent with the experimental results. Unexpectedly, the water molecules within the adjacent weak adsorption layer exhibit superdiffusive rotation, contrary to the conventional diffusive rotation of bulk water, while the vibrational motion maintains the characteristic of bulk water. The mechanism underlying this abnormal superdiffusive rotation is attributed to the translation-rotation decoupling of water, in which the translation is restrained by the strong hydrogen bonding within the bilayer interfacial water, whereas the rotation is accelerated freely by the asymmetric water environment. This superdiffusive rotation dynamics may elucidate the experimentally observed large fluctuation of the potential of zero charge on Pt and thereby the conventional Helmholtz layer model revised by including the contribution of interfacial water orientation. The surprising superdiffusive rotation of vicinal water next to noble metals will shed new light on the physicochemical processes and the activity of water molecules near metal electrodes or catalysts.

Elasticity of self-organized frustrated disordered spring networks.

There have been some interesting recent advances in understanding the notion of mechanical disorder in structural glasses and the statistical mechanics of these systems' low-energy excitations. Here we contribute to these advances by studying a minimal model for structural glasses' elasticity in which the degree of mechanical disorder-as characterized by recently introduced dimensionless quantifiers-is readily tunable over a very large range. We comprehensively investigate a number of scaling laws observed for various macro, meso and microscopic elastic properties, and rationalize them using scaling arguments. Interestingly, we demonstrate that the model features the universal quartic glassy vibrational density of states as seen in many atomistic and molecular models of structural glasses formed by cooling a melt. The emergence of this universal glassy spectrum highlights the role of self-organization (toward mechanical equilibrium) in its formation, and elucidates why models featuring structural frustration alone do not feature the same universal glassy spectrum. Finally, we discuss relations to existing work in the context of strain stiffening of elastic networks and of low-energy excitations in structural glasses, in addition to future research directions.

Superconductivity in Twisted Bismuth Bilayers

AbstractTwo twisted bismuth bilayers, TBB, each with 120 atoms, are studied using their electron density of states and their vibrational density of states using first‐principles calculations. Metallic character at the Fermi level is found for the non‐rotated sample as well as for each sample rotated 0.5°, 1.0°, 1.5°, 2.0°, 2.5°, 3.0°, 4.0°, 5.0°, 6.0°, 7.0°, 8.0°, and 10° with respect to each other. Assuming that the superconductivity is BCS‐type and the invariance of the Cooper pairing potential, a maximum superconducting temperature TC ≈1.8 K is predicted for a magic angle of 0.5° between the two bilayers, increasing the superconducting transition temperature from the experimentally measured value of 0.53 mK for the Wyckoff structure of crystalline bismuth.

On the molecular mechanisms of H2/N2 uptake in confined ionic liquids: A computational study

Classical molecular dynamics and hybrid grand canonical Monte Carlo/molecular dynamics simulations were combined to analyze the gas uptake mechanism of hydrogen and nitrogen molecules inside carbon nanotubes filled with an ionic liquid. Several nanotube diameters (from 6 Å to 12.24 Å) and two different ionic liquids (ethylammonium nitrate and 1-ethyl-3-methylimidazolium tetrafluoroborate) were considered to study their effect on the gas capture capacity and on the location of gas molecules within the nanotubes. The simulations showed that nitrogen absorption ability is, in general, greater than that of hydrogen, with the aprotic ionic liquid being more efficient for gas confinement. In addition, gas capture was observed to increase from a scarce 0.4% in bulk ionic liquids up to 8%-25% inside small nanotubes, and the maximum gas uptake was observed for those nanotubes that allow for a greater degree of conformational freedom of the ionic liquid. However, our calculations show that, whereas hydrogen storage is mainly governed by the amount of accessible free volume, for understanding that of nitrogen solvation energetics must be also considered. In all cases, gas molecules are absorbed in the ionic liquid-rich-region, but the interactions with the other components of the system favour their accommodation closer to the carbon wall than to the nanotube centre. Finally, single-particle dynamics of gas molecules was analyzed by means of the velocity autocorrelation functions and the vibrational density of states, which show a blue-shifting when increasing the radius of the nanotube.

The basic intermediate-range order structures in the FLiNaK–LaF3–Li2O melt: identification and characterisation

ABSTRACT In this paper, we investigate the structure of FLiNaK–LaF3 melt with small addition of Li2O through the theoretical approach combining ab initio molecular dynamics and simulation of the isolated structural units. The structure of the melt was studied in detail by calculation of radial distribution functions along with coordination numbers and radii. We found that oxyfluoride intermediate-range structure is formed in the melt. Our observations support the suggestions of other authors on formation of intermediate-range structures in fluoride melts containing metal oxides. Given structure shows long lifetime, the consideration of the isolated specie is valuable. We performed a simulation of ‘gas-phase’ [O2La4Fn] structure in order to calculate its Raman spectrum. It was found that the spectrum of the isolated structure agree in semi-quantitative manner with the vibrational density of states of the oxygen ions in the melt.

A comparative study on adiabatic and nonadiabatic dynamics of the H(2S) + NaH(X1Σ+) reaction

To reveal the influence of nonadiabatic couplings on the H(2S) + NaH(X1Σ+) reaction, a comparative study on adiabatic and nonadiabatic dynamics is conducted by using the time-dependent wave packet method. The dynamics results show that nonadiabatic couplings reduce the reactivity of H2(X1Σg+) forming channel and vibrational state density of the product, while the exchange reaction channel is almost unaffected. Although the nonadiabatic couplings have a great influence on the product state distribution, it has little influence on the scattering direction of the product. For the H2(X1Σg+) forming channels, products tend to forward scattering. For the exchange reaction channel, the NaH(X1Σ+) product exhibits a maximum scattering peak in the backward direction. The study reveals that the effect of nonadiabatic couplings on the ro-vibration distribution of the H2(X1Σg+) forming channel in the H(2S) + NaH(X1Σ+) reaction is significantly different from the effect in the H(2S) + LiH(X1Σ+) reaction.

Elastic and inelastic phonon scattering effects on thermal conductance across Au/graphene/Au interface

Heat dissipation from graphene devices is predominantly limited by heat conduction across the metal contacts with complex phonon scattering. In this work, the effects of elastic and inelastic phonon scattering on the interfacial thermal conductance (ITC) across the Au/graphene/Au interface are studied using both atomistic Green's function (AGF) and reverse non-equilibrium molecular dynamics methods. The results show that the contribution of inelastic phonon scattering to the ITC increases with the enhancement of interfacial bonding strength. Moreover, the overlap of the vibrational density of states across the interface shows that the coupling between the Au layer (adjacent to the Au/graphene interface) and graphene's out-of-plane modes plays the dominant role in ITC across the Au/graphene interface. By comparing the transmission functions calculated with AGF and spectral heat current decomposition methods, the inelastic phonon scattering process facilitates phonon transmission in the lower and higher frequency range but hinders phonon transmission in the intermediate frequency range. It is expected that this study can contribute to a better understanding of the thermal conduction mechanism across the metal/graphene interface, providing guidance for thermal management and heat conduction optimization of graphene in microelectronic devices.

Born-Oppenheimer Molecular Dynamics with a Linear Combination of Atomic Orbitals and Hybrid Functionals for Condensed Matter Simulations Made Possible. Theory and Performance for the Microcanonical and Canonical Ensembles.

The implementation of an original Born-Oppenheimer molecular dynamics module is presented, which is able to perform simulations of large and complex condensed phase systems for sufficiently long time scales at the level of density functional theory with hybrid functionals, in the microcanonical (NVE) and canonical (NVT) ensembles. The algorithm is fully integrated in the Crystal code, a program for quantum mechanical simulations of materials, whose peculiarity stems from the use of atom-centered basis functions within a linear combination of atomic orbitals to describe the wave function. The corresponding efficiency in the evaluation of the exact Fock exchange series has led to the implementation of a rich variety of hybrid density functionals at a low computational cost. In addition, the molecular dynamics implementation benefits also from the effective MPI parallelization of the code, suited to exploit high-performance computing resources available on current generation supercomputer architectures. Furthermore, the information contained in the trajectory of the dynamics is extracted through a series of postprocessing algorithms that provide the radial distribution function, the diffusion coefficient and the vibrational density of states. In this work, we present a detailed description of the theoretical framework and the algorithmic implementation, followed by a critical evaluation of the accuracy and parallel performance (e.g., strong and weak scaling) of this approach, when ice and liquid water simulations are performed in the microcanonical and canonical ensembles.

Low-Frequency Spectra of Hydrated Ionic Liquids with Kosmotropic and Chaotropic Anions.

In this study, we investigated the water concentration dependence of the intermolecular vibrations of two hydrated ionic liquids (ILs), cholinium dihydrogen phosphate ([ch][dhp]) and cholinium bromide ([ch]Br), using femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES). The anions of the former and latter hydrated ILs are kosmotropic and chaotropic, respectively. We found that the spectral peak of ∼50 cm-1 shifted to the low-frequency side in hydrated [ch][dhp], indicating the weakening of its intermolecular interactions. In contrast, no change in the peak frequency of the low-frequency band at ∼50 cm-1 was observed with increasing water concentration in hydrated [ch]Br. The vibrational density of states (VDOS) spectra generated from molecular dynamics (MD) simulations were in qualitative agreement with the experimental results. Decomposition analysis of the VDOS spectra for each component revealed that the red shift of the low-frequency band in the hydrated [ch][dhp] upon water addition was essentially due to the contributions of anions and water rather than that of the cholinium cation. We also found from the low-frequency spectra of the two hydrated ILs that they differed in the concentration dependence of the 180 cm-1 band, which is assigned as a hindered translational motion of water molecules combined to form O···O stretching motions. From the relationship between the peak frequency of the low-frequency band and the bulk parameter, which is the square root of the surface tension divided by the density, we found that the peak frequency in the hydrated IL with kosmotropic [dhp]- depends on the bulk parameter, similar to the case for an aqueous solution of the typical deep eutectic solvent reline. However, the peak frequency of the hydrated IL with chaotropic Br- is constant with the bulk parameter.

Glass-Like Phonon Dynamics and Thermal Transport in a GeTe Nano-Composite at Low Temperature.

In this work, the experimental evidence of glass-like phonon dynamics and thermal conductivity in a nanocomposite made of GeTe and amorphous carbon is reported, which is of interest for microelectronics, and specifically phase change memories. It is shown that, the total thermal conductivity is reduced by a factor of three at room temperature with respect to pure GeTe, due to the reduction of both electronic and phononic contributions. This latter, similarly to glasses, is small and weakly increasing with temperature between 100 and 300 K, indicating a mostly diffusive thermal transport and reaching a value of 0.86(7)Wm-1K-1 at room temperature. A thorough investigation of the nanocomposite's phonon dynamics reveals the appearance of an excess intensity in the low energy vibrational density of states, reminiscent of the Boson peak in glasses. These features can be understood in terms of an enhanced phonon scattering at the interfaces, due to the presence of elastic heterogeneities, at wavelengths in the 2-20 nm range. The findings confirm recent simulation results on crystalline/amorphous nanocomposites and open new perspectives in phonon and thermal engineering through the direct manipulation of elastic heterogeneities.

Boson peak in the vibrational spectra of glasses

A hallmark of glasses is an excess of low-frequency, nonphononic vibrations. It is manifested as a terahertz peak—the boson peak—in the ratio of the vibrational density of state (VDoS) and Debye's VDoS of phonons. Here, using experimental data, extensive computer simulations, and a mean-field model, we show that the nonphononic part of the VDoS itself features both a universal power-law tail and a peak at higher frequencies, entirely accounted for by quasilocalized nonphononic vibrations, whose existence and spectra power-law tail were recently established in computer glasses. We rationalize the variation of the peak's frequency and magnitude with glasses' thermal history, which is much weaker than the variation of the tail and may follow an opposite trend, and show that the peak's modes are composed of many spatially coupled quasilocalized nonphononic vibrations. Our results shed light on the origin, nature, and properties of the boson peak in glasses. Published by the American Physical Society 2024

Excess Density of Vibrational States at Terahertz Frequencies in the IR Spectra of Glassy Polymers

The IR spectra of glassy polymers were studied in the terahertz range 0.27 − 6 THz (9–200 cm−1), where absorption appears due to both individual and collective torsional (libration) vibrations preceding the manifestation of relaxation dynamics. It is shown that collective torsional-vibrational modes, caused by the correlation of librational vibrations in a section of the chain commensurate with its thermodynamic segment, are responsible for the excess density of vibrational states at terahertz frequencies in the IR spectra of glassy polymers.

Wettability-dependent thermal transport at the Fe nanoparticle-water interface: Molecular dynamics simulations

Nanoparticles are pivotal in applications such as solar thermal utilization, drug delivery, and water treatment. However, the microscopic mechanisms of heat transfer between nanoparticles and water, especially considering wettability effects, remain poorly understood. This study aims to investigate the interfacial heat transport properties of Fe nanoparticles-water using molecular dynamics simulations with varying levels of wettability. And the results indicate that the thermal conductance at the interface between Fe nanoparticles and water is 97.9 × 108 W/m2 K. The study also reveals an oscillatory pattern in the water density near the Fe nanoparticle interface, resulting in a distinct “double-density peak” With increased wettability, this peak density consistently grows, while the thickness of the adjacent solid-like layer remains relatively unchanged. Through the analysis of the vibrational density of states at the interface, the study reveals the microscopic mechanism by which wettability affects the thermal conductance of the Fe nanoparticles-water interface. Enhanced wettability improves the coupling of low-frequency phonon modes across the solid-liquid boundary, increasing thermal energy transfer efficiency. The study further identifies that low-frequency transverse modes play a vital role in heat transfer at the interface. Consequently, these insights provide a valuable theoretical framework for comprehending heat transport mechanisms at soft-hard interfaces.

Ab initio study of the vibrational spectra of amorphous boron nitride

Boron Nitride (BN) is an interesting polymorphic insulator that is commonly found in four different crystalline structures, each one with different electrical and mechanical properties which makes it an attractive material for technological and industrial applications. Seeking to improve its features, several experimental and simulational works have studied the amorphous phase (a-BN) focusing on electronic and structural properties, pressure-induced phase transformations, and a hydrogenated form of a-BN. By means of ab initio Molecular Dynamics and our well-proven amorphization process known as the undermelt-quench approach, herein three amorphous supercells were computationally generated, two with 216 atoms (densities of 2.04 and 2.80 g cm−3) and a third one with 254 atoms (density of 3.48 g cm−3). The topology, the vibrational density of states and some thermodynamic properties of the three samples are reported and compared with existing experiments and with other computational results.

Transferable Water Potentials Using Equivariant Neural Networks.

Machine learning interatomic potentials (MLIPs) have emerged as a technique that promises quantum theory accuracy for reduced cost. It has been proposed [J. Chem. Phys. 2023, 158, 084111] that MLIPs trained on solely liquid water data cannot accurately transfer to the vapor-liquid equilibrium while recovering the many-body decomposition (MBD) analysis of gas-phase water clusters. This suggests that MLIPs do not directly learn the physically correct interactions of water molecules, limiting transferability. In this work, we show that MLIPs using equivariant architecture and trained on 3200 liquid water structures reproduces liquid-phase water properties (e.g., density within 0.003 g/cm3 between 230 and 365 K), vapor-liquid equilibrium properties up to 550 K, the MBD analysis of gas-phase water cluster up to six-body interactions, and the relative energy and the vibrational density of states of ice phases. We show that potentials developed using equivariant MLIPs allow transferability for arbitrary phases of water that remain stable in nanosecond long simulations.

Toward Atomistic Understanding of Iron Phosphate Glass: A First-Principles-Based Density Functional Theory Modeling and Study of Its Physical Properties.

Iron phosphate glasses (IPGs) have been proposed as futuristic materials for nuclear waste immobilization and anode materials for lithium batteries. Recently, many attempts have been made to propose atomistic models of IPGs to explain their properties from an atomistic viewpoint. In this paper, we seek to produce small scale models of IPG that can be handled within the scheme of density functional theory (DFT) to study its electronic structure. The starting models, generated using the Monte Carlo (MC) method, were subsequently annealed using ab initio molecular dynamics (AIMD) to minimize the coordination defects. The geometry of the equilibrated structure was then optimized at 0 K. This hybrid approach (MC + AIMD + DFT optimization) produced good atomistic models of IPG, which can reproduce the experimentally observed band gap, vibrational density of states, magnetic moment of Fe, and mechanical and optical properties. Computationally expensive melt-quench simulation can be avoided using the present approach, allowing the use of DFT for accurate calculations of properties.

Vibrational spectrum of Granular packings with random matrices

The vibrational spectrum of granular packings can be used as a signature of the jamming transition, with the density of states at zero frequency becoming nonzero at the transition. It has been proposed previously that the vibrational spectrum of granular packings can be approximately obtained from random matrix theory. Here, we show that the autocorrelation function of the density of states shows good agreement between dynamical numerical simulations of frictionless bead packs near the jamming point and the analytic predictions of the Laguerre orthogonal ensemble of random matrices; there is clear disagreement with the Gaussian orthogonal ensemble, establishing that the Laguerre ensemble correctly reproduces the universal statistical properties of jammed granular matter and excluding the Gaussian orthogonal ensemble. We also present a random lattice model which is a physically motivated variant of the random matrix ensemble. Numerical calculations reveal that this model reproduces the known features of the vibrational density of states of frictionless granular matter, while also retaining the correlation structure seen in the Laguerre random matrix theory.Graphic abstract

Low-frequency vibrational density of states of ordinary and ultra-stable glasses

A remarkable feature of disordered solids distinct from crystals is the violation of the Debye scaling law of the low-frequency vibrational density of states. Because the low-frequency vibration is responsible for many properties of solids, it is crucial to elucidate it for disordered solids. Numerous recent studies have suggested power-law scalings of the low-frequency vibrational density of states, but the scaling exponent is currently under intensive debate. Here, by classifying disordered solids into stable and unstable ones, we find two distinct and robust scaling exponents for non-phononic modes at low frequencies. Using the competition of these two scalings, we clarify the variation of the scaling exponent and hence reconcile the debate. Via the study of both ordinary and ultra-stable glasses, our work reveals a comprehensive picture of the low-frequency vibration of disordered solids and sheds light on the low-frequency vibrational features of ultra-stable glasses on approaching the ideal glass.

Theoretical investigations of the vibrational spectra and hydrogen bond vibrations of two-dimensional ice I

In 2020, experimental observations of a stable two-dimensional (2D) ice I structure on a gold substrate were reported. As an atomic-level material, 2D ice has potential applications in many fields. However, the vibrational spectra of 2D ice I, including its infrared (IR) absorption, Raman scattering, and inelastic neutron-scattering spectra, have not been collected, owing to the complexity of the experimental conditions required to do so. We used first-principle density functional theory calculations to model 2D ice I and proved that it can stably exist without a gold substrate. We also simulated the vibrational phonon density of states and the IR and Raman spectra of 2D ice I. The vibrational frequencies in the translational band of 2D ice I were lower than those of 3D ice, owing to the hydrogen bonds of the former being weaker than those of the latter. The dynamic process analysis of hydrogen bonds showed that the vibrational modes of 2D ice I are quite different with that of 3D ice showing a different vibrational spectrum.

Investigating thermal conductivity and mechanical properties of a hybrid material based on cellulose nanofibers and boron nitride nanotubes using molecular dynamics simulations

Cellulose nanofibers (NFCs) have emerged as a preferred choice for fabricating nanomaterials with exceptional mechanical properties. At the same time, boron nitride nanotubes (BNNTs) have long been favored in thermal management devices due to their superior thermal conductivity (k). This study uses reverse non-equilibrium molecular dynamics (MD) simulations to investigate k for a hybrid material based on NFCs and BNNTs. The result is then compared with pure NFC and BNNT-based structures with equivalent total weight content to elucidate how incorporating BNNT fillers enhances k for the hybrid system. Furthermore, the fundamental phonon vibration modes responsible for driving thermal transport in NFC-based materials upon incorporating BNNTS are identified by computing the vibrational density of states from the Fourier transform analysis of the averaged mass-weighted velocity autocorrelation function. Additionally, MD simulations demonstrate how both NFCs and BNNTs synergistically improve the constituting hybrid structure’s mechanical properties (e.g. tensile strength and stiffness). The overarching aim is to contribute towards the engineered design of novel functional materials based on nanocellulose that simultaneously improve crucial physical properties pertaining to thermal transport and mechanics.