Surface Vibrational Modes Research Articles

3D 3,44T19 Type Carbon Allotrope (3,44T19‐CA): An Ideal Candidate with Phononic Stiefel–Whitney Topology and Multi–Dimensional Boundary Vibrational Modes

The Stiefel–Whitney (SW) insulator, which lacks spin‐orbit coupling and has space–time inversion () symmetry, has attracted significant interest due to its fragile topological state and unconventional bulk‐boundary correspondence. Previously, the identification of SW insulators has been widely proposed for 2D phononic systems, but it has received little attention for 3D phononic systems. Herein, it is recognized that the 3D 3,44T19 type carbon allotrope (3,44T19‐CA) possesses the possibility to attain the nontrivial phononic SW topology characterized by a nontrivial second SW number, specifically w2 = 1. In addition, the 3D 3,44T19‐CA has 2D surface vibrational modes and 1D hinge vibrational modes, providing an excellent platform for multi–dimensional topological phononic boundaries research.

Pressure Distributions in Glottal Geometries With Multichannel Airflows

Computer simulation of self-sustained oscillation of the vocal folds has been successful with application of simple Bernoulli-like driving pressures. As voice simulation is now applied to asymmetric vibration with complex mode structures that yield partial vocal fold contact, the driving pressures need refinement. Two independent approaches were used to obtain pressure distributions. The first was a high-fidelity immersed-boundary method computation and the second was a series of pressure tap measurements on scaled-up physical models. Glottal geometries were based on normal surface modes of vibration. Samples are chosen from a large inventory of measured and calculated profiles. Pressure distributions show the complexity that can exist in the driving forces on vocal fold surfaces. Qualitative similarity between computation and measurement was established for a variety of contact patterns, showing diverse pressure gradients in multiple directions. Simplified Bernoulli approaches to glottal pressure distributions are defensible when a single flow channel is preserved in vocal fold oscillation. However, when there are contact islands that produce confluence or difluence of multiple airflow channels, the pressure gradients vary profoundly. Small quantitative differences were observed between measurement and calculation, primarily due to spatial sampling.

Orientation Sensitive SEIRA Sensors Based on Single-Walled Carbon Nanotube Near Fields.

Molecular vibrations that bear information about intrinsic properties of chemical compounds are challenging to detect at submonolayer densities. Surface-enhanced infrared absorption (SEIRA) spectroscopy has been proven to be a viable approach to enhance and detect weak vibration signals. Here, we report a SEIRA sensor based on mid-infrared surface plasmon resonances supported by single-walled carbon nanotubes (SWCNTs). Due to the 1D nature of SWCNTs, their plasmon modes are highly polarized with the electromagnetic fields spatially confined to nanometer scales. Leveraging these characteristics of SWCNTs, we observe a polarization selective coupling between their surface plasmons and vibrational modes of chemical bonds introduced onto their surfaces. A maximum modulation of ∼15% to the plasmon resonance peak is obtained for a submonolayer chemical group coverage. These findings suggest that SWCNTs may potentially serve as a highly sensitive SEIRA platform for revealing intricate information about molecular compositions and bond orientations.

On the quantum dynamical treatment of surface vibrational modes for reactive scattering of H2 from Cu(111) at 925 K.

We construct the effective Hartree potential for H2 on Cu(111) as introduced in our earlier work [Dutta et al., J. Chem. Phys. 154, 104103 (2021), and Dutta et al., J. Chem. Phys. 157, 194112 (2022)] starting from the same gas-metal interaction potential obtained for 0K. Unlike in that work, we now explicitly account for surface expansion at 925K and investigate different models to describe the surface vibrational modes: (i) a cluster model yielding harmonic normal modes at 0K and (ii) slab models resulting in phonons at 0 and 925K according to the quasi-harmonic approximation-all consistently calculated at the density functional theory level with the same exchange-correlation potential. While performing dynamical calculations for the H2(v = 0, j = 0)-Cu(111) system employing Hartree potential constructed with 925K phonons and surface temperature, (i) the calculated chemisorption probabilities are the highest compared to the other approaches over the energy domain and (ii) the threshold for the reaction probability is the lowest, in close agreement with the experiment. Although the survival probabilities (v' = 0) depict the expected trend (lower in magnitude), the excitation probabilities (v' = 1) display a higher magnitude since the 925K phonons and surface temperature are more effective for the excitation process compared to the phonons/normal modes obtained from the other approaches investigated to describe the surface.

Polarization-resolved resonant Raman excitation of surface and bulk electronic bands and phonons in MBE-grown topological insulator thin films.

Interaction of phonons with Dirac-like electronic states sets the fundamental limit of electron transport in topological insulators (TIs). Polarization-resolved and resonant Raman scattering of bulk and surface electronic excitation and vibrational modes in Bi2Te3 and Bi2-xSbxTe3-ySey (BSTS) thin films was investigated. At photon energies (Ep) of 1.57 and 2.54 eV, A11g and A21g (LO) modes in Bi2Te3 and BSTS were resonantly excited owing to interband optical excitations of the surface Dirac state (DS) and bulk conduction band (CB), respectively. At room temperature, the resonance of the surface phonon of Raman and IR active modes E1u (LO) and A11u (LO) was observed in Bi2Te3 because of interband excitation of bulk CB, and interband transition of DS resonantly excited the A21u (LO) surface phonon in BSTS. A Fano line-shape suggested interference in the presence of electron-phonon coupling of the surface states.

Comprehensive scrutiny of surface mechanical parameters of graphyne-based materials for metal-ions and metal-air batteries applications: A perspective and a hybrid atomistic-continuum model

Graphyne family, as a low-dimensional carbon allotrope, is utilized for metal-ion and –air batteries as the anode and cathode materials due to their unique characteristics. These novel carbon nanomaterials can provide more theoretical storage capacity than graphene, while their specific surface mechanical parameters and vibrational frequencies can influence battery performance. However, there needs to be clear information that can explain the effects of these parameters on battery efficiency. In this respect, the influences of the surface elasticity, residual stress, density, vibrational modes, and frequencies of α, β, and γ-graphyne circular monolayers on anode and cathode materials have been investigated in current research using the hybrid molecular dynamics simulation and modified classical continuum mechanics methods. Concerning metal-ion batteries, the results disclose that the suitability sequence for anode materials can be expressed as γ-graphyne > graphene > β-graphyne > α-graphyne monolayers. In the case of metal-air batteries, the competence sequence for cathode materials is in the order of γ-graphyne > β-graphyne ∼ graphene > α-graphyne monolayers. Therefore, γ-graphyne with suitable storage capacity, low volume expansion, good surface elasticity, low surface residual stress, and appropriate specific surface area is the promising anode and cathode material for metal-ion and -air batteries, respectively.

Formulation of temperature dependent effective Hartree potential incorporating quadratic over linear molecular DOFs-surface modes couplings and its effect on quantum dynamics of D2 (v = 0, j = 0)/D2 (v = 0, j = 2) on Cu(111) metal surface

The effect of surface temperature on the scattering and dissociation processes of D2 (v = 0, j = 0)/D2 (v = 0, j = 2) on Cu(111) metal plane is investigated by formulating a time and temperature dependent effective Hamiltonian within mean-field approach, where the molecular degrees of freedom and surface mode vibrations are assumed to be weakly coupled with each other. While constructing such effective Hamiltonian with a Hartree product type wavefunction, we incorporate: (i) an operator algebra method to circumscribe higher order-quadratic (anharmonic) molecular DOFs-surface modes couplings over the linear coupling case implemented previously [Adhikari and coworkers, J. Chem. Phys. 154, 104103 (2021)]; (ii) surface temperature by considering Bose–Einstein or Maxwell–Boltzmann probability factors for the initial state distribution of the surface vibrational modes. Finally, a six-dimensional (6D) quantum dynamical (QD) calculation is performed with such newly formulated effective Hartree potential and calculated transition/dissociation probabilities at various surface temperature situations. The quadratic (anharmonic) molecular DOFs-surface modes couplings modify the reaction and transition probabilities substantially with change of surface temperature, which indicates the crucial role of surface mode vibrations on the molecule-surface scattering phenomena.

Infrared surface phonon nanospectroscopy of an interacting dielectric-particle–dielectric-substrate dimer using fast electrons

Refinements in energy monochromation and aberration correction in state-of-the-art scanning transmission electron microscopes has opened access to the far infrared regime for spectroscopic characterization at the nanoscale. At these low energies, the dielectric environment, such as a dielectric slab adjacent to the target specimen, may no longer play a passive role in the spectrum. Instead, the environment may itself host resonances that mix with those of the target and complicate interpretation of its spectral responses. This paper explores a theoretical description of the coupling between the collective vibrational surface modes of a dielectric particle and dielectric slab of varying thickness for the purpose of elucidating the interacting phononic excitations in dielectric materials typical of inelastic electron scattering measurements in the infrared. Dynamical coordinates and a governing Hamiltonian are rigorously defined in the quasistatic limit to account for phonon mode mixing and forcing by an aloof electron probe, which travels along a grazing trajectory, parallel to the dielectric slab. As the spectral window of interrogation by fast electron probes has been extended down to thermal energies with unprecedented meV energy resolution, theoretical models like that presented herein are crucial for accurate interpretation of experimental data.

Terahertz surface modes and electron-phonon coupling on Bi2Se3 (111)

We present a combined experimental and theoretical study of the surface vibrational modes of the topological insulator (TI) Bi$_2$Se$_3$ with particular emphasis on the low-energy region below 10 meV that has been difficult to resolve experimentally. By applying inelastic helium atom scattering (HAS), the entire phonon dispersion was determined and compared with density functional perturbation theory (DFPT) calculations. The intensity of the phonon modes is dominated by a strong Rayleigh mode, in contrast to previous experimental works. Moreover, also at variance with recent reports, no Kohn-anomaly is observed. These observations are in excellent agreement with DFPT calculations. Besides these results, the experimental data reveal$-$via bound-state resonance enhancement$-$two additional dispersion curves in the gap below the Rayleigh mode. They are possibly associated with an excitation of a surface electron density superstructure that we observe in HAS diffraction patterns. The electron-phonon coupling paramenter $\lambda$ = 0.23 derived from our temperature dependent Debye-Waller measurements compares well with values determined by angular resolved photoemission or Landau level spectroscopy. Our work opens up a new perspective for THz measurements on 2D materials as well as the investigation of subtle details (band bending, the presence of quantum well states) with respect to the electron-phonon coupling.

IMPACT OF Ni DOPANT ON OPTICAL AND MAGNETIC PROPERTIES OF ZnO NANOPARTICLES FOR BIOMEDICAL APPLICATIONS

In this work, Zn1-xNixO NPs with different concentration (x= 0.0, 0.03, 0.06 and 0.09) were synthesized by using co-precipitation method. The present study is related to investigate crystal structure, surface morphology, optical and magnetic behavior of pure and Ni dopant ZnO NPs. The hexagonal wurtzite structure and crystallite size (19.45 to 21.25 nm) was investigated by using XRD analysis.SEM and FTIR used to identify the surface morphology, stretching and vibrational modes of different functional groups (ZnO, OH, CO and H-O-H) attached on the spectrum of Ni dopant ZnO NPs. Moreover, the optical behavior of Ni dopant ZnO NPs was studied by UV-visible spectroscopy which indicates the absorption band of red shift. Finally, VSM analysis illustrated that Ni dopant ZnO NPs shows high magnetization, retentivity and low corecivity as compare to pure ZnO NPs. In an overall assessment the Ni dopant ZnO NPs shows better optical and magnetic properties for biomedical applications.

On size-dependent large-amplitude free oscillations of FGPM nanoshells incorporating vibrational mode interactions

At nanoscale, surface free energies of the atoms located on the free surfaces of structures significantly affect their mechanical characteristics. In this study, nonlinear large-amplitude free vibration response of nanoshells prepared from functionally graded porous materials (FGPM) is investigated by taking into account surface stress size effects and vibrational mode interactions. Non-classical shell model is constructed on the basis of the Gurtin–Murdoch type of the surface theory of elasticity having the capability of capturing surface stress size dependency. The accuracy of nonlinear vibration analysis is improved by incorporating the interaction of the main vibration mode and the first, third and fifth symmetric oscillation modes. Moreover, the closed-cell Gaussian-Random field scheme is put to use to extract the mechanical characteristics of FGPM nanoshell. Multiple timescales technique is then applied to achieve surface stress elastic-based nonlinear frequency of FGPM nanoshell analytically for different interactions between vibrational modes. It is revealed that by incorporating the interactions of the main vibration mode and higher symmetric oscillation modes, the behavior of the backbone curves belongs to the nonlinear free oscillation response of FGPM nanoshells changes from hardening to softening schema. It is found that when only the main vibration mode is taken into account, surface elasticity effects makes an enhancement in the significance of the hardening schema. However, by considering the interactions of higher symmetric oscillation modes, surface elasticity effects makes a reduction in the significance of the softening schema.

Role of oxygen concentrations on structural and optical properties of RF magnetron sputtered ZnO thin films

We report an investigation on the effect of oxygen flow rate on the structural and optical properties of zinc oxide thin films prepared by RF magnetron sputtering. The structural measurements were carried using grazing incidence X-ray diffraction, atomic force microscopy and Raman spectroscopy. The role of oxygen partial pressure on the crystallinity, the surface morphology and vibrational modes has been established. The optical properties of the films were investigated using FR-Basic-VIS/NIR fitted with FR-Monitor software for film thickness, refractive index and color determination. The film thickness is observed to increase when oxygen is introduced at 4 sccm but eventual decrease with increase in the flow rate an indication of initial increase in rate of deposition followed by reduction. Elaborate explanations of these trends are provided.

Investigation of Surface and Bulk Vibrational Modes in SiC Polytypes using Spatially Resolved Monochromated HREELS

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Investigation on structural, linear, nonlinear and optical limiting properties of sol-gel derived nanocrystalline Mg doped ZnO thin films for optoelectronic applications

Nanostructured thin films of pure as well as Mg-doped Zinc Oxide (MZO) were successfully casted on glass substrates through sol-gel technique. X-ray diffraction patterns display that all deposited films exhibit good crystallinity, hexagonal wurtzite structure and are preferentially grown along (002) plane (i.e. C-axis). Surface morphology, vibrational modes and optical properties were inspected by AFM, FT-Raman and UV–Visible–NIR spectroscopy. AFM Analysis revealed the uniform nanowire growth of MZO films where each nanowire was made up of very fine nanoparticles. The grain size was found to be increased from 16 to 25 nm with increasing the Mg-doping which agreed with the crystallite sizes obtained from the XRD analysis. The linear and nonlinear optical functionals were evaluated from optical data. Further, the deposited films were subjected to Z-scan measurement and studied its different key properties. The values of χ(3) is found to be enhanced from 0.27 × 10−8 to 4.36 × 10−8 due to Mg doping. The optical limiting threshold of MZO nanostructured films are also studied, and the obtained threshold values are found in the range 1.7 to 7.4 kJ/cm2. These low values suggests that the fabricated films can be used as optical limiters to protect sensor devices from high intensity light.

Atomic and Molecular Adsorption on Cu(111)

Due to the wide use of copper-based catalysts in industrial chemical processes, fundamental understanding of the interactions between copper surfaces and various reaction intermediates is highly desired. Here, we performed periodic, self-consistent density functional theory (DFT-GGA) calculations to study the adsorption of five atomic species (H, C, N, O, and S), seven molecular species (NH3, CH4, N2, CO, HCN, NO, and HCOOH), and 13 molecular fragments (CH, CH2, CH3, NH, NH2, OH, CN, COH, HCO, COOH, HCOO, NOH, and HNO) on the Cu(111) surface at a coverage of 0.25 monolayer. The preferred binding site, binding energy, and the corresponding surface deformation energy of each species were determined, as well as the estimated diffusion barrier and diffusion pathway. The binding strengths calculated using the PW91 functional decreased in the following order: CH > C > O > S > CN > NH > N > CH2 > OH > HCOO > COH > H > NH2 > NOH > COOH > HNO > HCO > CH3 > NO > CO > NH3 > HCOOH. No stable binding structures were observed for N2, HCN, and CH4. The adsorbate–surface and intramolecular vibrational modes of all the adsorbates at their preferred binding sites were deternined. Using the calculated adsorption energetics, potential energy surfaces were constructed for the direct decomposition of CO, CO2, NO, N2, NH3, and CH4 and the hydrogen-assisted decomposition of CO, CO2, and NO.

Inelastic vibrational bulk and surface losses of swift electrons in ionic nanostructures

In a recent paper [Lagos et al., Nature (London) 543, 533 (2017)] we have used electron energy loss spectroscopy with sub-10 meV energy and atomic spatial resolution to map optical and acoustic, bulk and surface vibrational modes in magnesium oxide nanocubes. We found that a local dielectric description works well for the simulation of aloof geometries, similar to related work for surface plasmons and surface plasmon polaritons, while for intersecting geometries such a description fails to reproduce the rich spectral features associated with excitation of bulk acoustic and optical phonons. To account for scatterings with a finite momentum exchange, in this paper we investigate molecular and lattice dynamics simulations of bulk losses in magnesium-oxide nanocubes using a rigid-ion description and investigate the loss spectra for intersecting electron beams. From our analysis we can evaluate the capability of electron energy loss spectroscopy for the investigation of phonon modes at the nanoscale, and we discuss shortcomings of our simplified approach as well as directions for future investigations.

Mapping vibrational surface and bulk modes in a single nanocube.

Imaging of vibrational excitations in and near nanostructures is essential for developing low-loss infrared nanophotonics, controlling heat transport in thermal nanodevices, inventing new thermoelectric materials and understanding nanoscale energy transport. Spatially resolved electron energy loss spectroscopy has previously been used to image plasmonic behaviour in nanostructures in an electron microscope, but hitherto it has not been possible to map vibrational modes directly in a single nanostructure, limiting our understanding of phonon coupling with photons and plasmons. Here we present spatial mapping of optical and acoustic, bulk and surface vibrational modes in magnesium oxide nanocubes using an atom-wide electron beam. We find that the energy and the symmetry of the surface polariton phonon modes depend on the size of the nanocubes, and that they are localized to the surfaces of the nanocube. We also observe a limiting of bulk phonon scattering in the presence of surface phonon modes. Most phonon spectroscopies are selectively sensitive to either surface or bulk excitations; therefore, by demonstrating the excitation of both bulk and surface vibrational modes using a single probe, our work represents advances in the detection and visualization of spatially confined surface and bulk phonons in nanostructures.

Transition from Molecular Vibrations to Phonons in Atomically Precise Cadmium Selenide Quantum Dots.

We use micro-Raman spectroscopy to measure the vibrational structure of the atomically precise cadmium selenide quantum dots Cd35Se20X30L30, Cd56Se35X42L42, and Cd84Se56X56L56. These quantum dots have benzoate (X) and n-butylamine (L) ligands and tetrahedral (Td) shape with edges that range from 1.7 to 2.6 nm in length. Investigating this previously unexplored size regime allows us to identify the transition from molecular vibrations to bulk phonons in cadmium selenide quantum dots for the first time. Room-temperature Raman spectra have broad CdSe peaks at 175 and 200 cm-1. Density functional theory calculations assign these peaks to molecular surface and interior vibrational modes, respectively, and show that the interior, surface, and ligand atom motion is strongly coupled. The interior peak intensity increases relative to the surface peak as the cluster size increases due to the relative increase in the polarizability of interior modes with quantum dot size. The Raman spectra do not change with temperature for molecular Cd35Se20X30L30, while the interior peak narrows and shifts to higher energy as temperature decreases for Cd84Se56X56L56, a spectral evolution typical of a phonon. This result shows that the single bulk unit cell contained within Cd84Se56X56L56 is sufficient to apply a phonon confinement model, and that Cd56Se35X42L42, with its 2.1 nm edge length, marks the boundary between molecular vibrations and phonons.

Thin InSb layers with metallic gratings: a novel platform for spectrally-selective THz plasmonic sensing.

We present a computational study of terahertz optical properties of a grating-coupled plasmonic structure based on micrometer-thin InSb layers. We find two strong absorption resonances that we interpret as standing surface plasmon modes and investigate their dispersion relations, dependence on InSb thickness, and the spatial distribution of the electric field. The observed surface plasmon modes are well described by a simple theory of the air/InSb/air tri-layer. The plasmonic response of the grating/InSb structure is highly sensitive to the dielectric environment and the presence of an analyte (e.g., lactose) at the InSb interface, which is promising for terahertz plasmonic sensor applications. We determine the sensor sensitivity to be 7200 nm per refractive index unit (or 0.06 THz per refractive index unit). The lower surface plasmon mode also exhibits a splitting when tuned in resonance with the vibrational mode of lactose at 1.37 THz. We propose that such interaction between surface plasmon and vibrational modes can be used as the basis for a new sensing modality that allows the detection of terahertz vibrational fingerprints of an analyte.

Effect of thermal treatment on Zn nanodisks

Metallic Zn nanodisks with hexagonal morphology were obtained onto glass substrate under vacuum thermal evaporation. A thermal characterization of Zn nanodiks showed a lower oxidation temperature than source powder Zn. Different thermal treatment on Zn nanodisks played an important role on the morphology, crystal size and surface vibrational modes of ZnO. The growth of ZnO nanoneedles started at the edge of metallic zinc hexagonal structures according with SEM images, the higher temperature the longer needles were grown. XRD diffractogram confirmed the wurtzite structure of ZnO with metallic nuclei. A wide band between 530 and 580 cm−1 of Raman scattering corresponded at surface vibrational modes not observed at higher temperature.