First-principles studies on the process of electron transfer between hydrophobic liquids and water.

Using the density functional theory, we conducted a study on the electrification upon contact between hydrophobic liquid molecules and water molecules, revealing localized characteristics of contact-electrification. These "localized features" refer to the specific microscale characteristics where electron transfer predominantly occurs at the contact regions, influenced by factors such as atomic distances and molecular orientations. Although the electrostatic potential and the highest occupied molecular orbital-lowest unoccupied molecular orbital gap offer substantial predictive insights for electron transfer across polymer interfaces, they fall short in capturing the complexities associated with the interaction between hydrophobic liquids and water molecules. The electronegativity of elements at the interface and the localization of molecular orbitals play a decisive role in electron transfer. Simultaneously, for liquid molecules with irregular structures, there is no correlation between the "contact area" and the amount of electron transfer. The "contact area" refers to the surface region where two different liquid molecules come into close proximity. It is defined by the surface area of atoms with interatomic distances smaller than the van der Waals radius. This study challenges traditional assumptions about contact-electrification, particularly in liquid-liquid interfaces, providing new insights into the localized nature of this phenomenon.

Understanding Contact Electrification at Water/Polymer Interface.

Contact electrification (CE) involves a complex interplay of physical interactions in realistic material systems. For this reason, scientific consensus on the qualitative and quantitative importance of different physical mechanisms on CE remains a formidable task. The CE mechanism at a water/polymer interface is a crucial challenge owing to the poor understanding of charge transfer at the atomic level. First-principle density functional theory (DFT), used in the present work, proposes a new paradigm to address CE. Our results indicate that CE follows the same trend as the gap between the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) of polymers. Electron transfer occurs at the outmost atomic layer of the water/polymer interface and is closely linked to the functional groups and atom locations. When the polymer chains are parallel to the water layer, most electrons are transferred; conversely, if they are perpendicular to each other, the transfer of charges can be ignored. We demonstrate that a decrease in the interface distance between water and the polymer chains leads to CE in quantitative agreement with the electron cloud overlap model. We finally use DFT calculations to predict the properties of CE materials and their potential for triboelectric nanogenerator energy harvesting devices.

On chain models for contact electrification.

An exact analytical model of charge dynamics for a chain of atoms with asymmetric hopping terms is presented. Analytic and numeric results are shown to give rise to similar dynamics in both the absence and presence of electron interactions. The chain model is further extended to the case of two atoms per cell (a perfect alloy system). This extension is further applied to contact electrification between two different atomic chains and the effect of increasing the magnitude of the contact transfer matrix element is studied.

Resonance photogeneration of hot electrons through Tamm surface states.

Internal surface photoemission of electrons from 1D crystal into a barrier with participation of Tamm state (TS) at the interface crystal barrier is considered theoretically for the first time, to the best of our knowledge. It is shown that resonant tunneling of electrons through a TS could lead to substantial enhancement of the quantum efficiency and lowering the red border to a value defined by the TS. In contrast to the Fowler quadratic law, the photocurrent scales linearly with photon energy near the red border. The results suggest that the efficiency of hot electron generation with plasmonic metal nanoparticles could reach several tens of percent, which is very attractive for application in energy conversion technologies such as water splitting.

Anomalous Topological Edge States in Non-Hermitian Piezophononic Media.

The bulk-boundary or bulk-edge correspondence is a principle relating surface confined states to the topological classification of the bulk. By marrying non-Hermitian ingredients in terms of gain or loss with media that violate reciprocity, an unconventional non-Bloch bulk-boundary correspondence leads to unusual localization of bulk states at boundaries-a phenomenon coined non-Hermitian skin effect. Here, we numerically employ the acoustoelectric effect in electrically biased and layered piezophononic media as a solid framework for non-Hermitian and nonreciprocal topological mechanics in the MHz regime. Thanks to a non-Hermitian skin effect for mechanical vibrations, we find that the bulk bands of finite systems are highly sensitive to the type of crystal termination, which indicates a failure of using traditional Bloch bands to predict the wave characteristics. More surprisingly, when reversing the electrical bias, we unveil how topological edge and bulk vibrations can be harnessed either at the same or opposite interfaces. Yet, while bulk states are found to display this unconventional skin effect, we further discuss how in-gap edge states in the same instant, counterintuitively are able to delocalize along the entire layered medium. We foresee that our predictions will stimulate new avenues in echo-less ultrasonics based on exotic wave physics.

Shape- and size dependent piezoelectric properties of monolayer hexagonal boron nitride nanosheets.

We use molecular dynamics simulations (MD) to study piezoelectric properties of hexagonal boron nitride nanosheets (BNNS) and reveal how piezoelectric properties depend on size and shape. We first analyze how the macroscopic shape affects the full 2D structure symmetry and its piezoelectric tensor. In particular, we demonstrate that a hexagonal (rectangular)-shaped BNNS belongs to the hexagonal 6̄m2 (monoclinic m) point group. Our simulation results show that the piezoelectric constants of BNNS depend strongly on the macroscopic shape, in agreement with the symmetry of the structure, but are nearly independent of the macroscopic size. The present study provides a detailed understanding of the piezoelectric properties of finite size BNNS and guidance to future experiments and optimization of 2D piezoelectric materials in general.

Contact Electrification by Quantum-Mechanical Tunneling.

A simple model of charge transfer by loss-less quantum-mechanical tunneling between two solids is proposed. The model is applicable to electron transport and contact electrification between e.g. a metal and a dielectric solid. Based on a one-dimensional effective-mass Hamiltonian, the tunneling transmission coefficient of electrons through a barrier from one solid to another solid is calculated analytically. The transport rate (current) of electrons is found using the Tsu-Esaki equation and accounting for different Fermi functions of the two solids. We show that the tunneling dynamics is very sensitive to the vacuum potential versus the two solids conduction-band edges and the thickness of the vacuum gap. The relevant time constants for tunneling and contact electrification, relevant for triboelectricity, can vary over several orders of magnitude when the vacuum gap changes by one order of magnitude, say, 1 Å to 10 Å. Coulomb repulsion between electrons on the left and right material surfaces is accounted for in the tunneling dynamics.

3D continuum phonon model for group-IV 2D materials.

A general three-dimensional continuum model of phonons in two-dimensional materials is developed. Our first-principles derivation includes full consideration of the lattice anisotropy and flexural modes perpendicular to the layers and can thus be applied to any two-dimensional material. In this paper, we use the model to not only compare the phonon spectra among the group-IV materials but also to study whether these phonons differ from those of a compound material such as molybdenum disulfide. The origin of quadratic modes is clarified. Mode coupling for both graphene and silicene is obtained, contrary to previous works. Our model allows us to predict the existence of confined optical phonon modes for the group-IV materials but not for molybdenum disulfide. A comparison of the long-wavelength modes to density-functional results is included.

A theory of generalized Bloch oscillations.

Bloch oscillations of electrons are shown to occur for cases when the energy spectrum does not consist of the traditional evenly-spaced ladders and the potential gradient does not result from an external electric field. A theory of such generalized Bloch oscillations is presented and an exact calculation is given to confirm this phenomenon. Our results allow for a greater freedom of design for experimentally observing Bloch oscillations. For strongly coupled oscillator systems displaying Bloch oscillations, it is further demonstrated that reordering of oscillators leads to destruction of Bloch oscillations. We stipulate that the presented theory of generalized Bloch oscillations can be extended to other systems such as acoustics and photonics.

Maximum absorption by homogeneous magneto-dielectric sphere.

In order to obtain a benchmark for electromagnetic energy harvesting, we investigate the maximum absorption efficiency by a magneto-dielectric homogeneous sphere illuminated by a plane wave, and we arrive at several novel results. For electrically small spheres we show that the optimal relative permeability and permeability of materials where ϵ(r)', µ(r)'≥1 is (1+i3) independent of sphere size, while that of metamaterials is (-2+iδ), where the imaginary part δ decreases strongly with decreasing sphere size. For larger spheres we show that while maximum absorption efficiency occurs at the resonances of the spherical modes, there exists a wide plateau of high absorption efficiency when material intrinsic impedance is constant; in the case of free-space intrinsic impedance and electrical radius κ=1, the absorption efficiency becomes 2.8. The investigation is analytic/numerical and based on the Lorenz-Mie theory combined with the optical theorem.

̀Spatial impulse response of a rectangular double curved transducer.

Calculation of the pressure field from transducers with both a convex and a concave surface geometry is a complicated assignment that often is accomplished by subdividing the transducer surface into smaller flat elements of which the spatial impulse response is known. This method is often applied to curved transducers because an analytical solution is unknown. In this work a semi-analytical algorithm for the exact solution to a first order in diffraction effect of the spatial impulse response of rectangular-shaped double curved transducers is presented. The solution and an approximation to it are investigated. The approximation reformulates the solution to an analytically integrable expression, which is computationally efficient to solve. Simulation results are compared to FIELD II simulations. Calculating the response from 200 different points yields a mean error for the different approximations ranging from 0.03% to 0.8% relative to a numerical solution for the spatial impulse response. It is also shown that the presented algorithm gives consistent results with FIELD II for a linear flat, a linear focused, and a convex nonfocused element. The solution involved a three-point Taylor expansion and gave an accuracy of 0.01%.

Plasmonic metamaterial wave retarders in reflection by orthogonally oriented detuned electrical dipoles.

We demonstrate that a pair of perpendicular electrical dipolar scatterers resonating at different frequencies can be used as a metamaterial unit cell to construct a nanometer-thin retarder in reflection, designing nanocross and nanobrick plasmonic configurations to function as reflecting quarter-wave plates at ~1520 and 770 nm, respectively. The design is corroborated experimentally with a monolayer of gold nanobricks, transforming linearly polarized incident radiation into circularly polarized radiation at ~780 nm.

Modeling transducer impulse responses for predicting calibrated pressure pulses with the ultrasound simulation program Field II.

Field II is a simulation software capable of predicting the field pressure in front of transducers having any complicated geometry. A calibrated prediction with this program is, however, dependent on an exact voltage-to-surface acceleration impulse response of the transducer. Such impulse response is not calculated by Field II. This work investigates the usability of combining a one-dimensional multilayer transducer modeling principle with the Field II software. Multilayer here refers to a transducer composed of several material layers. Measurements of pressure and current from Pz27 piezoceramic disks as well as pressure and intensity measurements in front of a 128 element commercial convex medical transducer are compared to the simulations. Results show that the models can predict the pressure from the piezoceramic disks with a root mean square (rms) error of 11.2% to 36.2% with a 2 dB amplitude decrease. The current through the external driving circuits are predicted within 8.6% to 36% rms error. Prediction errors of 30% and in the range of 5.8%-19.9% for the pressure and the intensity, respectively, are found when simulating the commercial transducer. It is concluded that the multilayer transducer model and the Field II software in combination give good agreement with measurements.

Detuned electrical dipoles for plasmonic sensing.

We demonstrate that a pair of electrical dipolar scatterers resonating at different frequencies, i.e., detuned electrical dipoles, can be advantageously employed for plasmonic sensing of the environment, both as an individual subwavelength-sized sensor and as a unit cell of a periodic array. It is shown that the usage of the ratio between the powers of light scattered into opposite directions (or into different diffraction orders), which peaks at the intermediate frequency, allows one to reach a sensitivity of ≈ 400 nm/RIU with record high levels of figure of merit exceeding 200. Qualitative considerations are supported with detailed simulations and proof-of-principle experiments using lithographically fabricated gold nanorods with resonances at 800 nm.

Modeling of nonlinear responses for reciprocal transducers involving polarization switching.

Nonlinearities and hysteresis effects in a reciprocal PZT transducer are examined by use of a dynamical mathematical model on the basis of phase-transition theory. In particular, we consider the perovskite piezoelectric ceramic in which the polarization process in the material can be modeled by Landau theory for the first-order phase transformation, in which each polarization state is associated with a minimum of the Landau free-energy function. Nonlinear constitutive laws are obtained by using thermodynamical equilibrium conditions, and hysteretic behavior of the material can be modeled intrinsically. The time-dependent Ginzburg-Landau theory is used in the parameter identification involving hysteresis effects. We use the Chebyshev collocation method in the numerical simulations. The elastic field is assumed to be coupled linearly with other fields, and the nonlinearity is in the E-D coupling. We present numerical results for the reciprocal-transducer system and identify the influence of nonlinearities on the system dynamics at high and low frequency as well as electrical impedance effects due to tuning by a series inductance. It is found that nonlinear effects are not important at high frequencies (1 MHz) subject to high-input voltages, but they become important under high-voltage and off-resonance conditions.

Vibration of piezoelectric elements surrounded by fluid media.

In this paper we analyse vibrational characteristics of piezoceramic shells surrounded by acoustic media. Main results are presented for radially polarized piezoceramic PZT5 elements of hollow cylindrical shapes. The coupling in the radial direction between the solid and the acoustic media is accounted for indirectly, via impedance boundary conditions. The model based on such impedance boundary condition approximations offers a robust simplified alternative to a full scale fluid-solid interaction modelling. By using this model, we analyse numerically the influence of the boundary conditions imposed in the axial direction for long, medium, and short (disk-like) piezoceramic elements.