Perturbed Charge Density Research Articles

Alloy informatics through ab initio charge density profiles: Case study of hydrogen effects in face-centred cubic crystals

Materials design has traditionally evolved through trial-error approaches, mainly due to the non-local relationship between microstructures and properties such as strength and toughness. We propose ‘alloy informatics’ as a machine learning based prototype predictive approach for alloys and compounds, using electron charge density profiles derived from first-principle calculations. We demonstrate this framework in the case of hydrogen interstitials in face-centred cubic crystals, showing that their differential electron charge density profiles capture crystal properties and defect-crystal interaction properties. Radial Distribution Functions (RDFs) of defect-induced differential charge density perturbations highlight the resulting screening effect, and, together with hydrogen Bader charges, strongly correlate to a large set of atomic properties of the metal species forming the bulk crystal. We observe the spontaneous emergence of classes of charge responses while coarse-graining over crystal compositions. Nudge-Elastic-Band calculations show that RDFs and charge features also connect to hydrogen migration energy barriers between interstitial sites. Unsupervised machine-learning on RDFs supports classification, unveiling compositional and configurational non-localities in the similarities of the perturbed densities. Electron charge density perturbations may be considered as bias-free descriptors for a large variety of defects.

Averaging over atom snapshots in linear-response TDDFT of disordered systems: A case study of warm dense hydrogen.

Linear-response time-dependent density functional theory (LR-TDDFT) simulations of disordered extended systems require averaging over different snapshots of ion configurations to minimize finite size effects due to the snapshot-dependence of the electronic density response function and related properties. We present a consistent scheme for the computation of the macroscopic Kohn-Sham (KS) density response function connecting an average over snapshot values of charge density perturbations to the averaged values of KS potential variations. This allows us to formulate the LR-TDDFT within the adiabatic (static) approximation for the exchange-correlation (XC) kernel for disordered systems, where the static XC kernel is computed using the direct perturbation method [Moldabekov et al., J. Chem. Theory Comput. 19, 1286 (2023)]. The presented approach allows one to compute the macroscopic dynamic density response function as well as the dielectric function with a static XC kernel generated for any available XC functional. The application of the developed workflow is demonstrated for the example of warm dense hydrogen. The presented approach is applicable for various types of extended disordered systems, such as warm dense matter, liquid metals, and dense plasmas.

Excitation of terahertz surface magnetoplasmons by nonlinear mixing of laser and its second harmonic on a rippled surface of n type semiconductor

We investigated the excitation of terahertz (THz) surface magneto plasmons (SMPs) by nonlinear mixing of laser and its second harmonic on a rippled surface of n-type semiconductor-free space interface. Obliquely incident p-polarized lasers exert a nonlinear ponderomotive force on free electrons of n-type semiconductor. Nonlinear ponderomotive force induces the oscillatory velocities at frequencies \(2\omega _{1}\) and (\(\omega _{1}-\omega _{2}\)). These oscillatory velocities beat the modulated electron density \(n_{q}\) to get the charge density perturbation at (\(2\omega _{1}, 2k_{1z}+q\)) and (\(\omega _{1}-\omega _{2}, k_{1z}-k_{2z}+q\)). Perturbed charge density couples with the linear oscillatory velocities to produce a nonlinear current density, which resonantly derives THz SMPs at frequency \(\omega =2\omega _{1}-\omega _{2}\) and propagation constant \(k_{z}=2k_{1z}-k_{2z}+q\). Here, q provides the extra wave number for the phase matching condition. The efficiency of THz SMPs wave amplitude was attained up to \(9\%\) and THz SMPs wave amplitude controlled by the electron cyclotron frequency \(\omega _{ce}\) and incident angle \(\theta\).

Flux-driven algebraic damping of m = 2 diocotron mode

Experiments with pure electron plasmas in a Malmberg–Penning trap have observed linear in time, algebraic damping of m = 2 diocotron modes. Transport due to small field asymmetries produces a low-density halo of electrons moving radially outward from the plasma core, and the mode damping begins when the halo reaches the resonant radius of the mode. The damping rate is proportional to the flux of halo particles through the resonant layer. The damping is related to, but distinct from spatial Landau damping in which a linear wave–particle resonance produces exponential damping. This paper reports an analytic theory that captures the main signatures reported for this novel damping, namely, that the damping begins when the halo particles reach the resonant radius and that the damping is algebraic in time with nearly constant damping rate. The model also predicts a nonlinear frequency shift. The model provides two ways to think about the damping. It results from a transfer of canonical angular momentum from the mode to halo particles being swept by the mode field through the nonlinear cat's eye orbits of the resonant region. More mechanistically, the electric field produced by the perturbed charge density of the resonant particles acts back on the plasma core causing E×B drift that gives rise to the damping and nonlinear frequency shift.

A new mechanism of direct coupling of laser energy to ions

The well-known schemes (e.g. Brunel mechanism, resonance absorption, heating etc) couple laser energy to the lighter electron species of the plasma. In this work, a fundamentally new mechanism of laser energy absorption directly to the heavier ion species has been proposed. The mechanism relies on the difference between the drifts of electron and ions in the oscillating electric field of the laser and an external magnetic field to create charge density perturbations. The proposed mechanism is verified with the help of particle-in-cell (PIC) simulations using OSIRIS4.0.

First-principles calculations of transition metal solute interactions with hydrogen in tungsten

We have performed systematic first-principles calculations to predict the interaction between transition metal (TM) solutes and hydrogen in the interstitial site as well as the vacancy in tungsten. We showed that the site preference of the hydrogen atom is significantly influenced by the solute atoms, which can be traced to the charge density perturbation in the vicinity of the solute atom. The solute-H interactions are mostly attractive except for Re, which can be well understood in terms of the competition between the chemical and elastic interactions. The chemical interaction dominates the solute-H interaction for the TM solutes with a large atomic volume and small electronegativity compared to tungsten, while the elastic interaction is primarily responsible for the solute-H interaction for the TM solutes with a small atomic volume and large electronegativity relative to tungsten. The presence of a hydrogen atom near the solute atom has a negative effect on the binding of other hydrogen atoms. The large positive binding energies among the solute, vacancy and hydrogen suggest that they would easily form a defect cluster in tungsten, where the solute-vacancy and vacancy-H interaction contribute greatly while the solute-H interaction contributes a little. Our result provides a sound theoretical explanation for recent experimental phenomena of hydrogen retention in the tungsten alloy and further recommends a suitable W–Re–Ta ternary alloy for possible plasma-facing materials (PFMs) including the consideration of the hydrogen retention.

Hydrogel charge regulation and electrolyte ion-concentration perturbations in nanoparticle gel electrophoresis

Gel electrophoresis of spherical nanoparticles (NPs) is studied using an electrokinetic model that couples the ion conservation equations to the Poisson and fluid momentum equations, thus including the so-called polarization and relaxation processes. This model is therefore the charged gel electrophoresis analogue of the well-known O’Brien and White solution of the standard electrokinetic model for free-solution electrophoresis. Results are provided for the small NPs (size around 10 nm) to which gel electrophoresis is relevant, because particles must be small enough to permeate the gel: these include the particle drag coefficient (or Brownian diffusivity), which is subject to hydrodynamic screening and electroviscous effects, and the electrophoretic mobility, which is subject to nonlinear electrostatic and charge polarization influences. Also addressed are the influences of charge-regulating gels and the accompanying particle-induced immobile charge-density perturbations. Ion-concentration perturbations attenuate the electrophoretic mobility and enhance the drag coefficient according to the particle charge and the mobility of the most abundant counterion. However, dynamic regulation of the hydrogel charge—termed the secondary immobile charge-density perturbation—has a negligible influence on the particle mobility, and may therefore be neglected for most practical purposes.

The perturbation energy: A missing key to understand the "nobleness" of bulk gold.

The nobleness of gold surfaces has been appreciated since long before the beginning of recorded history. Yet, the origin of this phenomenon remains open because the so far existing explanations either incorrectly imply that silver should be the noblest metal or would fail to predict the dissolution of Au in aqua regia. Here, based on our analyses of oxygen adsorption, we advance that bulk gold's unique resistance to oxidation is traced to the large energy cost associated with the perturbation its surfaces undergo upon adsorption of highly electronegative species. This fact is related to the almost totally filled d-band of Au and relativistic effects, but does not imply that the strength of the adsorbate-Au bond is weak. The magnitude of the structural and charge-density perturbation energy upon adsorption of atomic oxygen—which is largest for Au—is assessed from first-principles calculations and confirmed via a multiple regression analysis of the binding energy of oxygen on metal surfaces.

Properties of dispersive Alfven waves: 4. Hydrodynamics (finite and high-pressure plasmas)

The behavior of dispersive Alfven waves (DAWs) in astrophysical plasmas of finite and high pressure, which have not been considered thus far, is studied in the hydrodynamic approximation. The results are analyzed and compared with those obtained in the kinetic approach. It is shown that one general solution for DAWs in plasmas of finite and high pressure can be obtained using the hydrodynamic approach in contrast to the kinetic one. Kinetic and hydrodynamic solutions correspond to each other very well in a domain with weakly damped DAWs; however, solutions may differ appreciably in some parameter domains, especially in high-pressure plasma. The effect of parameters of the astrophysical medium on the DAW behavior and properties is analyzed. All the main wave characteristics were determined: dispersion, damping, polarization, density perturbations, and charge density perturbations. Since finite-pressure plasma is one of the most frequently encountered states of astrophysical plasma, it is very important to take into account specific features in behavior of these waves for their detecting and a more correct understanding of their behavior and the role they play in different astrophysical processes that occur in space environment.

Properties of dispersive Alfvén waves: 3. Hydrodynamics (Very Low, Intermediate, and Low Density Plasmas)

The behavior of dispersive Alfven waves (DAWs), including inertial and kinetic Alfven waves, in astrophysical plasmas of very low, intermediate, and low pressure is investigated in the hydrodynamic approximation. New full solutions are obtained. Our results are analyzed and compared with those from the kinetic approach. It is shown that one general solution for the DAWs in plasmas of very low, intermediate, and low pressure can be obtained in the framework of the hydrodynamic approach, as opposed to the kinetic one. In the very low damping region, the kinetic and hydrodynamic solutions agree very well; but there are parameter regions where the solutions are essentially different. The influence of the astrophysical medium parameters on the DAW behavior and properties is analyzed. All main wave characteristics—the dispersion, damping, polarization, density perturbations, and charge density perturbations—are obtained, whose the consideration is very important for the observation and detection of these waves, as well as for a more correct understanding of their behavior and role in various astrophysical processes taking place in the cosmic medium.

Nanoparticle gel electrophoresis: Soft spheres in polyelectrolyte hydrogels under the Debye–Hückel approximation

A mathematical model for electrophoresis of polyelectrolyte coated nanoparticles (soft spheres) in polyelectrolyte hydrogels is proposed, and evaluated by comparison to literature models for bare-sphere gel electrophoresis and free-solution electrophoresis. The utilities of approximations based on the bare-particle electrophoretic mobility, free-solution mobility, and electroosmotic flow in hydrogels are explored. Noteworthy are the influences of the particle–core dielectric constant and overlap of the polyelectrolyte shell. The present theory, which neglects ion-concentration and charge-density perturbations, indicates that the gel electrophoretic mobilities of metallic-core nanoparticles in polyelectrolyte gels can be qualitatively different than for their non-metallic counterparts. These insights will be beneficial for interpreting nanoparticle gel-electrophoresis data, optimizing electrophoretic separations, and engineering nanoparticles for technological applications.

Properties of dispersive Alfvén waves: 2. Kinetics (finite and high density plasmas)

The work is devoted to the study of the behavior of dispersive Alfven waves in astrophysical plasma of finite and high pressure. All the main wave characteristics were obtained, namely, the dispersion, fading, polarization, density perturbations, and charge density perturbations. The effect of the parameters of the space environment on the behavior and properties of dispersive Alfven waves was analyzed. The wave behavior in finite and high-pressure plasmas is shown to differ appreciably from the behavior in very low, intermediate, and low-pressure plasmas.

Properties of dispersive Alfvén waves: 1. Kinetics (very low, intermediate, and low density plasmas)

The work is devoted to the study of the behavior of dispersive Alfven waves, including inertial and kinetic Alfven waves, in astrophysical plasma of very low, intermediate, and low pressure. New and full solutions were obtained. The solutions for “ordinary” and inertial Alfven waves were shown to be particular cases of the general solution. The effect of the parameters of the astrophysical medium on the behavior and properties of dispersive Alfven waves was analyzed. All the main wave characteristics were obtained, namely, the dispersion, fading, polarization, density perturbations, and charge density perturbations, whose consideration is essential for observation and detection of these waves and for more adequate understanding of their role in different astrophysical processes that occur in the space environment.

Photoinduced Dynamics in the Charge Density Wave Compound 4HB-TaSe2

We report on ultrafast photoindued charge density wave (CDW) dynamics in the transition-metal dichalcogenide 4Hb -TaSe2 , studied with ultrafast electron diffraction. Fluence dependence of the lattice superstructure suppression show a phase transition from the commensurate to the incommensurate phase of 4Hb -TaSe2 . Unusually long recovery times of perturbed charge density waves indicate th importance of a coupling between the two dimensional CDWs.

Spin- and charge density perturbations and short-range order in Fe–Cu and Fe–Zn BCC alloys: A Mössbauer study

A model used to describe the 57Fe Mössbauer spectra for the binary BCC iron alloys rich in iron has been extended to account for the alloy crystallographic ordering. The ordering is accounted for by introducing single order parameter. Extension of the model is described in detail. The model has been tested applying it to the Fe–Cu alloys obtained by the arc melting and to the Fe–Zn alloys prepared by the solid state reaction. Random alloys are obtained up to ∼2 at% of Cu, and up to ∼8 at% of Zn. For higher impurity (minor alloy component) concentration it has been found that Cu atoms try to avoid Fe atoms in the iron matrix as nearest neighbors, while the opposite happens to the Zn atoms, albeit at much lesser scale, i.e., Zn–Zn interactions are much weaker than Fe–Zn interactions at the nearest neighbor distance. Perturbations to the iron magnetic hyperfine field (spin density) and electron (charge) density on the iron nucleus have been obtained for both series of alloys versus impurity concentration.

Charge and Spin Density Perturbation on Iron Nuclei by Non-Magnetic Impurities Substituted on the Iron Sites in α-Fe

The paper is aimed at the review of the charge and spin density perturbation on the iron nucleus in the BCC iron-based binary alloys containing as the impurity either 4d (Nb, Mo, Ru, Rh, Pd) or 5d (Os, Ir, Au) metals. Additionally Ga has been used as such impurity as well. Measurements have been performed by means of the Fe 57 transmission Mossbauer spectroscopy at room temperature. Powder X-ray diffraction data for alloys investigated show linear dependence of the lattice constant versus impurity concentration. Mossbauer data were treated assuming random distribution of the impurity over the iron sites and additive effect for the charge density perturbation, and additive in the algebraic sense effect for the corresponding spin density perturbation. Hence, the effect of impurity depends solely on the distance between impurity and the iron nucleus under above assumptions. It has been found that impurities being further away than a third or in some cases as the second neighbor do not contribute directly to the charge and spin perturbation. On the other hand, they have usually some minor effect on the average charge and spin density. Generally, the perturbation to either charge or spin density has some oscillatory character versus distance from the impurity. The phase and period of the charge oscillation is vastly different from the phase and period of the spin oscillation in the majority of cases. Substitution of the impurities with the increasing number of 4d or 5d electrons leads to the lowering of the electron density on the iron nucleus and causes decreased band spin density on this nucleus. Subsequent impurities donate more and more d-type electrons to the band, and the latter screen more and more effectively s-like electrons. Hence, the density of the s-like electrons on the iron nucleus diminishes. Impurities with 5d electrons have generally stronger effect on the charge and spin density perturbation than impurities with 4d electrons.

Static and dynamic second hyperpolarizability calculated by time-dependent density functional cubic response theory with local contribution and natural bond orbital analysis

The static and dynamic second hyperpolarizability gamma has been investigated by time-dependent density functional cubic response theory. The third-order coupled perturbed Kohn-Sham equations were solved to obtain the third-order perturbed charge density. Calculations on a number of small molecules (N(2), CO(2), C(2)H(4), CO, HF, H(2)O, and CH(4)), paradisubstituted oligoacetylene chains, benzene, and eight paradisubstituted benzenes were performed to verify the implementation and to assess the accuracy of the nonhybrid and hybrid time-dependent density functional theory computations. Nitroaniline and a derivative were taken as examples to investigate the distribution of the "gamma density" and to demonstrate the feasibility of analyzing cubic response functions in terms of contributions from natural bond orbitals (NBOs) and natural localized molecular orbitals (NLMOs). The results highlight the contributions from atoms and bonds on different functional groups to the total value of gamma based on the NBO/NLMO analysis, which might be helpful for new nonlinear optical materials design.

Study of static and dynamic first hyperpolarizabilities using time-dependent density functional quadratic response theory with local contribution and natural bond orbital analysis

We apply time-dependent density-functional quadratic response theory to investigate the static and dynamic second-order polarizabilities (first hyperpolarizability) beta. A new implementation using Slater-type basis functions, numerical integration, and density fitting techniques is reported. The second order coupled perturbed Kohn-Sham equations are solved and the second-order perturbed charge density is obtained. It is useful to highlight atomic and bond contributions to understand the relation between molecular structure and properties. Four moderately sized molecules (para-nitroaniline and derivatives thereof) are investigated to assess the accuracy of the time-dependent density-functional theory computations and to investigate the distribution of the second-order charge density as well as the "beta density." Our results highlight the contributions from atoms and bonds on different functional groups to the total value of beta with Mulliken-type and natural bond orbital (NBO) analyses, and demonstrate in some cases how contributions from a particular bond may be identified easily by visual inspection of the beta density. In addition, the position of side group substitution on carbon-carbon bonds significantly affects the hyperpolarizability. A contribution analysis as performed here might be helpful for the design of new materials with desired properties.

How single conjugated polymer molecules respond to electric fields

Conjugated polymers find applications in a range of devices such as light-emitting diodes, field-effect transistors and solar cells. The elementary electronic response of these semiconductors to electric fields is understood in terms of nanoscale perturbations of charge density. We demonstrate a general breaking of spatial charge symmetry by considering the linear Stark effect in the emission of single chromophores on individual chains. Spectral shifts of several nanometres occur due to effective dipoles exceeding 10 D. Although the electric field does not ionize the exciton, some molecules exhibit field-induced intensity modulations. This quenching illustrates the equivalence of charge symmetry breaking and polaron-pair or charge-transfer-state formation, and provides a microscopic picture of permanent charging, which leads to doping and exciton dissociation in actual devices. In addition to using this tuneable emission in single-photon electro-optic modulators, hysteresis in the Stark shift suggests a route to designing nanoscale memory elements such as molecular switches.

Driven phase space holes and synchronized Bernstein, Greene, and Kruskal modes

The excitation of synchronized Bernstein, Greene, and Kruskal (BGK) modes in a pure electron plasma confined in Malmberg–Penning trap is studied. The modes are excited by controlling the frequency of an oscillating external potential. Initially, the drive resonates with, and phase-locks to, a group of axially bouncing electrons in the trap. These initially phase-locked electrons remain phase-locked (in “autoresonance”) during a subsequent downward chirp of the external potential’s oscillation frequency. Only a few new particles are added to the resonant group as the frequency, and, hence, the resonance, moves to lower velocities in phase space. Consequently, the downward chirp creates a charge density perturbation (a hole) in the electron phase space distribution. The hole oscillates in space, and its associated induced electric field constitutes a BGK mode synchronized with the drive. The size of the hole in phase space, and thus the amplitude of the mode, are largely controlled by only two external parameters: the driving frequency and amplitude. A simplified kinetic theory of this excitation process is developed. The dependence of the excited BGK mode amplitude on the driving frequency chirp rate and other plasma parameters is discussed and theoretical predictions are compared with recent experiments and computer simulations.