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We experimentally investigate phase shift gained by electromagnetic radiation transmitted through a two-dimensional electron system (2DES) on a dielectric substrate. We systematically examined the dependence of the phase shift on the radiation frequency and 2DES electron density for the GaAs semiconductor substrate. A theoretical approach was developed that found good agreement with experimental results. We demonstrate a practically achievable phase shift of 105 °. Obtained findings pave the way for the design of terahertz devices that can manipulate the radiation phase in a controlled and precise manner. [ABSTRACT FROM AUTHOR]

Quantum-chemical subsystem and embedding methods require complex workflows that may involve multiple quantum-chemical program packages. Moreover, such workflows require the exchange of voluminous data that go beyond simple quantities, such as molecular structures and energies. Here, we describe our approach for addressing this interoperability challenge by exchanging electron densities and embedding potentials as grid-based data. We describe the approach that we have implemented to this end in a dedicated code, PyEmbed, currently part of a Python scripting framework. We discuss how it has facilitated the development of quantum-chemical subsystem and embedding methods and highlight several applications that have been enabled by PyEmbed, including wave-function theory (WFT) in density-functional theory (DFT) embedding schemes mixing non-relativistic and relativistic electronic structure methods, real-time time-dependent DFT-in-DFT approaches, the density-based many-body expansion, and workflows including real-space data analysis and visualization. Our approach demonstrates, in particular, the merits of exchanging (complex) grid-based data and, in general, the potential of modular software development in quantum chemistry, which hinges upon libraries that facilitate interoperability. [ABSTRACT FROM AUTHOR]

A finite element simulation model of terahertz wave propagation in plasma is developed. The equivalence of treating the plasma as a dielectric and an electrical conductor is studied in comparison. The propagation characteristics of terahertz waves in a unmagnetized plasma obtained from experimental measurements or simulations are simulated by interpolating the distribution of key parameters such as electron density and collision frequency of the external plasma. The validity of this open simulation model is verified by using the simulation data of plasma electron density generated by the independent electrochemical plasma generation model as external data. Using this model as a research tool, the propagation characteristics of terahertz waves in plasma measured by laser Thomson scattering are studied. The simulation results of the terahertz wave propagation characteristics in the plasma with and without considering the collision frequency are compared by this model. The terahertz transmission model in plasma can be used to study the propagation characteristics of terahertz waves in various inhomogeneous plasmas, which would be helpful to solve the communication "blackout" problem. [ABSTRACT FROM AUTHOR]

Despite the importance of the one-particle picture provided by the orbital paradigm, a rigorous understanding of the spatial distribution of electrons in molecules is still of paramount importance to chemistry. Considerable progress has been made following the introduction of topological approaches, capable of partitioning space into chemically meaningful regions. They usually provide atomic partitions, for example, through the attraction basins of the electron density in the quantum theory of atoms in molecules (QTAIM) or electron-pair decompositions, as in the case of the electron localization function (ELF). In both cases, the so-called electron distribution functions (EDFs) provide a rich statistical description of the electron distribution in these spatial domains. Here, we take the EDF concept to a new fine-grained limit by calculating EDFs in the QTAIM ∩ ELF intersection domains. As shown in AHn systems based on main group elements, as well as in the CO, NO, and BeO molecules, this approach provides an exquisitely detailed picture of the electron distribution in molecules, allowing for an insightful combination of the distribution of electrons between Lewis entities (such as bonds and lone pairs) and atoms at the same time. Besides mean-field calculations, we also explore the impact of electron correlation through Hartree–Fock (HF), density functional theory (DFT) (B3LYP), and CASSCF calculations. [ABSTRACT FROM AUTHOR]

This study investigates the sensitive region and safe operation voltage of single-event burnout (SEB) in lateral depletion-mode Ga2O3 MOSFET devices via technology computer aided design simulation. Based on the distribution of the electric field, carrier concentration, and electron current density when SEB occurs, the radiation damage mechanism of SEB is proposed. The mechanism of SEB in Ga2O3 MOSFET was revealed to be the result of a unique structure without a PN junction within it, which possesses gate control ability and exerts a significant influence on the conduction of the depletion region. [ABSTRACT FROM AUTHOR]

Porphyrins are prime candidates for a host of molecular electronics applications. Understanding the electronic structure and the role of anchoring groups on porphyrins is a prerequisite for researchers to comprehend their role in molecular devices at the molecular junction interface. Here, we use the density functional theory approach to investigate the influence of anchoring groups on Ni and Zn diphenylporphyrin molecules. The changes in geometry, electronic structure, and electronic descriptors were evaluated. There are minimal changes observed in geometry when changing the metal from Ni to Zn and the anchoring group. However, we find that the distribution of electron density changes when changing the anchoring group in the highest occupied and lowest unoccupied molecular orbitals. This has a direct effect on electronic descriptors such as global hardness, softness, and electrophilicity. Additionally, the optical spectra of both Ni and Zn diphenylporphyrin molecules exhibit either blue or red shifts when changing the anchoring group. These results indicate the importance of the anchoring group on the electronic structure and optical properties of porphyrin molecules. [ABSTRACT FROM AUTHOR]

Laser Thomson scattering is a minimally intrusive diagnostic technique for determining electron temperature, density, and bulk velocity in plasma systems. Advances in technology have made possible the application of Thomson scattering to electric propulsion-relevant plasma systems, with reported electron number-density detection limits as low as 1 × 10 16 m − 3 , and electron temperatures from one-to-tens eV. However, the implementation of laser Thomson scattering in large vacuum testing facilities, wherein electric propulsion devices are tested, remains a challenge. This work presents the implementation of a laser Thomson scattering system in a large vacuum test facility at the Georgia Tech High Power Electric Propulsion Laboratory. The diagnostic was optimized for maximum light-collection efficiency and ease of re-alignment while the facility is at vacuum. The high light-collection efficiency allowed reduced accumulation times to achieve the target detection limit of 1 × 10 17 m − 3 . The diagnostic is used to measure axial electron property profiles in the near-field plume of a lanthanum hexaboride hollow cathode operating at 25 A on krypton at a background pressure of 1.3 × 10 − 6 Torr—Kr. The diagnostic is quantitatively compared to similar systems in the literature. The resulting axial points, collected from 2 to 8 mm downstream of the cathode keeper orifice, are qualitatively and quantitatively compared with simulations and experimental measurements made with electrostatic probes and laser-induced fluorescence. The main quantitative difference between measured values and results is the one to two order of magnitude difference in the peak electron density, being attributed to the relative size and location of the external anode with respect to the cathode keeper. [ABSTRACT FROM AUTHOR]

The significance of solvent effects in electronic structure calculations has long been noted, and various methods have been developed to consider this effect. The reference interaction site model self-consistent field with constrained spatial electron density (RISM-SCF-cSED) is a hybrid model that combines the integral equation theory of molecular liquids with quantum chemistry. This method can consider the statistically convergent solvent distribution at a significantly lower cost than molecular dynamics simulations. Because the RISM theory explicitly considers the solvent structure, it performs well for systems where hydrogen bonds are formed between the solute and solvent molecules, which is a challenge for continuum solvent models. Taking advantage of being founded on the variational principle, theoretical developments have been made in calculating various properties and incorporating electron correlation effects. In this review, we organize the theoretical aspects of RISM-SCF-cSED and its distinctions from other hybrid methods involving integral equation theories. Furthermore, we carefully present its progress in terms of theoretical developments and recent applications. [ABSTRACT FROM AUTHOR]

In density-functional theory, the exchange–correlation (XC) energy can be defined exactly through the coupling-constant (λ) averaged XC hole n ̄ xc (r , r ′ ) , representing the probability depletion of finding an electron at r′ due to an electron at r. Accurate knowledge of n ̄ xc (r , r ′ ) has been crucial for developing XC energy density-functional approximations and understanding their performance for molecules and materials. However, there are very few systems for which accurate XC holes have been calculated since this requires evaluating the one- and two-particle reduced density matrices for a reference wave function over a range of λ while the electron density remains fixed at the physical (λ = 1) density. Although the coupled-cluster singles and doubles (CCSD) method can yield exact results for a two-electron system in the complete basis set limit, it cannot capture the electron–electron cusp using finite basis sets. Focusing on Hooke's atom as a two-electron model system for which certain analytic solutions are known, we examine the effect of this cusp error on the XC hole calculated using CCSD. The Lieb functional is calculated at a range of coupling constants to determine the λ-integrated XC hole. Our results indicate that, for Hooke's atoms, the error introduced by the description of the electron–electron cusp using Gaussian basis sets at the CCSD level is negligible compared to the basis set incompleteness error. The system-, angle-, and coupling-constant-averaged XC holes are also calculated and provide a benchmark against which the Perdew–Burke–Ernzerhof and local density approximation XC hole models are assessed. [ABSTRACT FROM AUTHOR]

Parr and Ghosh [Phys. Rev. A. 51 3564 (1995)] demonstrated that when near-exact electron densities and potentials are used, the exchange–correlation energies of first- and second-row atoms are well-described by a combination of the Fermi–Amaldi functional with a functional that is homogeneous of degree one under density scaling. Insight into this observation is provided by considering their work from the perspective of the effective homogeneity of the overall exchange–correlation functional. By considering a general form that combines the Fermi–Amaldi functional with a functional that is homogeneous of degree k, it is shown that for these atoms, the functional of Parr and Ghosh (k = 1) exhibits essentially optimal effective homogeneities on the electron-deficient side of the integer. Percentage errors in effective homogeneities are close to percentage errors in exchange–correlation energies. [ABSTRACT FROM AUTHOR]

The intrinsic carrier density of 4H-SiC at temperatures ranging from 294 to 595 K was derived by analyzing a collector current in an npn-type SiC bipolar junction transistor, the structure of which was designed based on a device simulation. The obtained intrinsic carrier density was in good agreement with the value calculated from the bandgap and effective densities of states taking multiple and non-parabolic SiC bands into account. The coincidence of the intrinsic carrier density obtained by these two different approaches indicates the usefulness of the proposed method and the validity of the evaluated value of intrinsic carrier density. The temperature dependence of the bandgap was also estimated from the deduced intrinsic carrier density and compared with an empirical formula. The derived bandgap agreed well with the empirical formula showing bandgap shrinkage at high temperatures. The errors in evaluating the intrinsic carrier density and the bandgap caused by the estimation of the hole density and electron mobility in the base layer are also discussed for the proposed method. [ABSTRACT FROM AUTHOR]

Machine learning (ML) of kinetic energy functionals (KEFs), in particular kinetic energy density (KED) functionals, is a promising way to construct KEFs for orbital-free density functional theory (DFT). Neural networks and kernel methods including Gaussian process regression (GPR) have been used to learn Kohn–Sham (KS) KED from density-based descriptors derived from KS DFT calculations. The descriptors are typically expressed as functions of different powers and derivatives of the electron density. This can generate large and extremely unevenly distributed datasets, which complicates effective application of ML techniques. Very uneven data distributions require many training datapoints, can cause overfitting, and can ultimately lower the quality of an ML KED model. We show that one can produce more accurate ML models from fewer data by working with smoothed density-dependent variables and KED. Smoothing palliates the issue of very uneven data distributions and associated difficulties of sampling while retaining enough spatial structure necessary for working within the paradigm of KEDF. We use GPR as a function of smoothed terms of the fourth order gradient expansion and KS effective potential and obtain accurate and stable (with respect to different random choices of training points) kinetic energy models for Al, Mg, and Si simultaneously from as few as 2000 samples (about 0.3% of the total KS DFT data). In particular, accuracies on the order of 1% in a measure of the quality of energy–volume dependence B ′ = E V 0 − Δ V − 2 E V 0 + E ( V 0 + Δ V) Δ V / V 0 2 (where V0 is the equilibrium volume and ΔV is a deviation from it) are obtained simultaneously for all three materials. [ABSTRACT FROM AUTHOR]

The topology of the Ehrenfest force field (EhF) is investigated as a tool for describing local interactions in molecules and intermolecular complexes. The EhF is obtained by integrating the electronic force operator over the coordinates of all but one electron, which requires knowledge of both the electron density and the reduced pair density. For stationary states, the EhF can also be obtained as minus the divergence of the kinetic stress tensor, although this approach leads to well-documented erroneous asymptotic behavior at large distances from the nuclei. It is shown that these pathologies disappear using the electron density functions and that the EhF thus obtained displays the correct behavior in real space, with no spurious critical points or attractors. Therefore, its critical points can be unambiguously obtained and classified. Test cases, including strained molecules, isomerization reactions, and intermolecular interactions, were analyzed. Various chemically relevant facts are highlighted: for example, non-nuclear attractors are generally absent, potential hydrogen–hydrogen interactions are detected in crowded systems, and a bifurcation mechanism is observed in the isomerization of HCN. Moreover, the EhF atomic basins are less charged than those of the electron density. Although integration of the EhF over regions of real space can also be performed to yield the corresponding atomic forces, several numerical drawbacks still need to be solved if electron density functions are to be used for that purpose. Overall, the results obtained support the Ehrenfest force field as a reliable descriptor for the definition of atomic basins and molecular structure. [ABSTRACT FROM AUTHOR]

Standard approximations for the exchange–correlation functional in Kohn–Sham density functional theory (KS-DFT) typically lead to unacceptably large errors when applied to strongly correlated electronic systems. Partition-DFT (PDFT) is a formally exact reformulation of KS-DFT in which the ground-state density and energy of a system are obtained through self-consistent calculations on isolated fragments, with a partition energy representing inter-fragment interactions. Here, we show how typical errors of the local density approximation (LDA) in KS-DFT can be largely suppressed through a simple approximation, the multi-fragment overlap approximation (MFOA), for the partition energy in PDFT. Our method is illustrated on simple models of one-dimensional strongly correlated linear hydrogen chains. The MFOA, when used in combination with the LDA for the fragments, improves LDA dissociation curves of hydrogen chains and produces results that are comparable to those of spin-unrestricted LDA, but without breaking the spin symmetry. MFOA also induces a correction to the LDA electron density that partially captures the correct density dimerization in strongly correlated hydrogen chains. Moreover, with an additional correction to the partition energy that is specific to the one-dimensional LDA, the approximation is shown to produce dissociation energies in quantitative agreement with calculations based on the density matrix renormalization group method. [ABSTRACT FROM AUTHOR]

The Air-breathing Microwave Plasma CAThode (AMPCAT) has been developed for air-breathing electric propulsion in very-low Earth orbit. In this study, the standalone AMPCAT plasma characteristics are analyzed by means of several diagnostic tools and operation on xenon is compared to a conventional hollow cathode. A transition of AMPCAT extracted current from a lower (< 0.1 A) to higher-current (> --> 0.5 A) mode, triggered by increasing the negative cathode bias voltage, is accompanied by a significant rise in internal electron density and external electron temperature. The AMPCAT is coupled with a cylindrical Hall thruster in the 100–300 W power-level running on 0.5–0.7 mg/s of xenon, and the thrust is directly measured for cathode operation with both xenon and air. Stable thruster operation is demonstrated for the AMPCAT running on both propellants. For xenon, the performance is compared to a hollow cathode, which reveals matching discharge current profiles but a significantly higher thrust for the AMPCAT at low discharge voltages, approximately two times higher at 200 V. Langmuir probe measurements highlight a 30–40 V lower plasma potential in the cathode vicinity for the AMPCAT with xenon compared to both the hollow cathode and AMPCAT with air. This indicates a significantly improved coupling of cathode electrons to the thruster discharge, yielding an increased degree of ionization. Faraday probe and Wien filter results show that a larger current utilization efficiency drives the observed performance difference at low discharge voltages, rather than a significant change in ion acceleration or plume divergence. [ABSTRACT FROM AUTHOR]

Practical density functional theory (DFT) owes its success to the groundbreaking work of Kohn and Sham that introduced the exact calculation of the non-interacting kinetic energy of the electrons using an auxiliary mean-field system. However, the full power of DFT will not be unleashed until the exact relationship between the electron density and the non-interacting kinetic energy is found. Various attempts have been made to approximate this functional, similar to the exchange–correlation functional, with much less success due to the larger contribution of kinetic energy and its more non-local nature. In this work, we propose a new and efficient regularization method to train density functionals based on deep neural networks, with particular interest in the kinetic-energy functional. The method is tested on (effectively) one-dimensional systems, including the hydrogen chain, non-interacting electrons, and atoms of the first two periods, with excellent results. For atomic systems, the generalizability of the regularization method is demonstrated by training also an exchange–correlation functional, and the contrasting nature of the two functionals is discussed from a machine-learning perspective. [ABSTRACT FROM AUTHOR]

Oxygen vacancies in indium tin oxide (ITO) thin films provide a direct route to effectively tune the free electron density and thereby, controlling the epsilon-near-zero (ENZ) cut-off wavelength, the wavelength at which the real part of permittivity crosses zero of the permittivity axis. In this report, oxygen vacancies in pulsed laser deposited ITO thin films are systematically tuned using different background gases (O 2 , N 2 , Ar, and He). ENZ cut-offs are observed for the films deposited under He and Ar gases. In contrast, no such cut-offs are observed in the case of other two gases. An ITO thin film deposited under He gas exhibits deeper resonance signal than the one deposited under Ar gas. As expected, no such dip in the resonance spectra is observed for the films deposited under O 2 and N 2 gases. This observation is directly correlated to the change in the number of oxygen vacancies under different ambient gases. A modified transfer matrix method which incorporates surface roughness as an effective medium layer is developed to describe the experimentally observed resonance spectra numerically. Angular invariancy of ENZ plasmon resonance and the difference in absorption values for ITO films deposited under different gases is understood in terms of local field intensity enhancement factor. The study presented here will certainly be very useful in understanding the ENZ plasmon resonance phenomena as a whole. Additionally, ITO films deposited under an inert gas environment could be excellent material platforms for realizing several exotic ENZ applications. [ABSTRACT FROM AUTHOR]

Orbital-Free Density-Functional Theory (OF-DFT) is known to represent a promising alternative to the standard Kohn-Sham (KS) DFT, as it relies on the electron density alone, without the need to calculate all KS single-particle orbitals and energies. Here, we investigate the behavior of the main ingredients of this theory, which are the non-interacting kinetic-energy density (KED) and the Pauli potential, for metal slabs. We derive explicit density functionals for these quantities in the quantum limit where all electrons are in the same slab discrete level of energy, and we present numerical calculations beyond this quantum limit for slabs of various widths. We have found the first explicit KED functional for a realistic many-particle fermionic system, which we prove to be generally valid with no assumption about the KS potential. We also discuss the total non-interacting kinetic energy and the corresponding enhancement factor, which represent basic quantities for the practical implementation of OF-DFT. [ABSTRACT FROM AUTHOR]

The Kohn-Sham theory addresses the challenge of representing the kinetic energy by re-quantizing density functional theory at a level of non-interacting electrons. It transforms the many-electron problem into a fictitious non-interacting electron problem, with the many-electron effects concealed within the exchange-correlation (XC) energy, which is expressed in terms of the electron density ρ(r). Unlike the wave function, ρ(r) can be viewed as a classical quantity, and expressing the XC energy in terms of it circumvents the need for correlated wave functions. In this work, we once again employ the re-quantization strategy and determine the XC energy using a local one-particle Schrödinger equation. The ground-state eigenfunction of the corresponding Hamiltonian is a reference point (r) dependent orbital φr,σ(u, σ′) which is subsequently used to generate the XC hole and the XC energy. The spin coordinate is denoted by σ and u is the electron-electron separation. The one-particle equation for φr,σ(u, σ′) includes a local potential vr,σ(u, σ′) that we approximate using two simple physical constraints. We assess the approximation by applying it to the helium iso-electronic series, the homogeneous electron gas, and the dissociation of the hydrogen molecule. [ABSTRACT FROM AUTHOR]

Orbital-free density functional theory (OF-DFT) holds promise to compute ground state molecular properties at minimal cost. However, it has been held back by our inability to compute the kinetic energy as a functional of electron density alone. Here, we set out to learn the kinetic energy functional from ground truth provided by the more expensive Kohn–Sham density functional theory. Such learning is confronted with two key challenges: Giving the model sufficient expressivity and spatial context while limiting the memory footprint to afford computations on a GPU and creating a sufficiently broad distribution of training data to enable iterative density optimization even when starting from a poor initial guess. In response, we introduce KineticNet, an equivariant deep neural network architecture based on point convolutions adapted to the prediction of quantities on molecular quadrature grids. Important contributions include convolution filters with sufficient spatial resolution in the vicinity of nuclear cusp, an atom-centric sparse but expressive architecture that relays information across multiple bond lengths, and a new strategy to generate varied training data by finding ground state densities in the face of perturbations by a random external potential. KineticNet achieves, for the first time, chemical accuracy of the learned functionals across input densities and geometries of tiny molecules. For two-electron systems, we additionally demonstrate OF-DFT density optimization with chemical accuracy. [ABSTRACT FROM AUTHOR]

The Fermi–Amaldi correction to the electrostatic self-repulsion of the particle density is usually regarded as a semi-classical exchange functional that happens to be exact only for one- and closed-shell two-electron systems. We show that this functional can be derived quantum-mechanically and is exact for any number of fermions or bosons of arbitrary spin as long as the particles occupy the same spatial orbital. The Fermi–Amaldi functional is also size-consistent for such systems, provided that the factor N in its expression is understood as an orbital occupation number rather than the total number of particles. These properties of the Fermi–Amaldi functional are ultimately related to the fact that it is a special case of the self-exchange energy formula. Implications of our findings are discussed. [ABSTRACT FROM AUTHOR]

In a recent study, we developed a kinetic-energy density functional that can be utilized in orbital-free quantum mechanical/molecular mechanical (OF-QM/MM) simulations. The functional includes the nonlocal term constructed from the response function of the reference system of the QM solute. The present work provides a method to combine the OF-QM/MM with a theory of solutions based on the energy representation to compute the solvation free energy of the QM solute in solution. The method is applied to the calculation of the solvation free energy Δμ of a QM water solute in an MM water solvent. It is demonstrated that Δμ is computed as −7.7 kcal/mol, in good agreement with an experimental value of −6.3 kcal/mol. We also develop a theory to map the free energy δμ due to electron density polarization onto the coordinate space of electrons. The free energy density obtained by the free-energy mapping for the QM water clarifies that each hydrogen atom makes a positive contribution (+34.7 kcal/mol) to δμ, and the oxygen atom gives the negative free energy (−71.7 kcal/mol). It is shown that the small polarization free energy −2.4 kcal/mol is generated as a result of the cancellation of these counteracting energies. These analyses are made possible by the OF-QM/MM approach combined with a statistical theory of solutions. [ABSTRACT FROM AUTHOR]

Atmospheric pressure plasmas generated from a helium gas with admixtures of water vapor have numerous applications in biomedicine. It is important that the chemistry of such plasmas can be tightly controlled so that they may be tailored for their intended use. In this study, computational modeling is used to vary the pulse repetition frequency of a nanosecond-pulsed, pin-to-pin He + 0.25% H 2 O discharge in the range of 1–100 kHz to determine the influence of the pulse repetition frequency on the resulting densities of reactive oxygen species and the rates of dominant reaction pathways involving them. The plasma is simulated using the 0D plasma-chemical kinetics model GlobalKin. The pulse shape is kept constant. The afterglow duration is, therefore, dependent on the repetition frequency. Analysis of the bulk plasma chemistry after the plasma has reached equilibrium shows that the peak electron density is only weakly dependent on the pulse repetition frequency. Increasing the pulse repetition frequency is shown to increase the density of H, O, and OH radicals, while the relationship between the repetition frequency and the densities of species with longer lifetimes, namely, H 2 O 2 and O 3 , is found to be more complex. These are formed throughout the afterglow, and their density depends on the availability of reactant species, the afterglow duration, and the background gas temperature. This work concludes that the pulse repetition frequency is not a simple control parameter, especially for species that are predominantly produced in the afterglow. Detailed modeling is required for accurate control of species densities using the pulse repetition frequency. [ABSTRACT FROM AUTHOR]

We have calculated the theoretical terahertz spectrum of the amino acid l-tyrosine using density functional theory (DFT). We tried two electron density functionals, Perdew–Burke–Ernzerhof (PBE) and PBE-d3. PBE-d3 includes dispersion corrections to build in van der Waals interactions, which play a role in intermolecular bonding. Both DFT models predicted a low-frequency mode that has not been previously reported. We designed an experiment to search for this mode. Using a deliberately thick sample, intense synchrotron radiation, low temperatures, and temperature variation has enabled us to observe a new resonance at 1.79 ±0.01 THz. While the PBE and PBE-d3 spectra are similar and both match the low-energy experimental data, overall the PBE-d3 appears to be slightly superior. Further refinement still of the functional may lead to even better agreement with experiment above 2.4 THz. [ABSTRACT FROM AUTHOR]

The first finite basis set implementation of the real-time time-dependent self-consistent field method in a dynamic (time-dependent) magnetic field using London atomic orbitals (LAOs) is presented. The accuracy of the finite basis approach using LAOs is benchmarked against numerical results from the literature for the hydrogen atom and H2 in the presence of rapidly oscillating magnetic fields. This comparison is used to inform the choice of appropriate basis sets for studies under such conditions. Remarkably, relatively modest compact LAO basis sets are sufficient to obtain accurate results. Analysis of electron dynamics in the hydrogen atom shows that LAO calculations correctly capture the time evolution of orbital occupations. The Fourier transformation of the autocorrelation function yields a power spectrum exhibiting harmonics associated with coherent emission, which closely matches the literature and further confirms the accuracy of this approach. The dynamical response of the electron density in H2 for a magnetic field parallel to the internuclear axis shows similar behavior to benchmark studies. The flexibility of this implementation is then demonstrated by considering how the dynamical response changes as a function of the orientation of the molecule relative to the applied field. At non-parallel orientations, the symmetry of the system is lowered and numerical benchmark data, which exploit cylindrical symmetry, are no-longer readily available. The present study demonstrates the utility of LAO-based calculations for extreme dynamic magnetic fields, providing a stress-test on the choice of basis. Future applications of this approach for less extreme dynamic magnetic fields are briefly discussed. [ABSTRACT FROM AUTHOR]

We present the chemical bonding and electronic properties of liquid methane at temperatures from 2000 to 4000 K and high densities of up to 3.0 g/cm3, calculated using ab initio molecular dynamics simulations in combination with the Mulliken population analysis. Bond-overlap populations and pair distribution functions are studied to investigate the evolution of electron delocalization accompanying atomic structure change as the density is increased. In addition, we also investigated the bandgap energy, electronic density of states, and spatial distribution of electron density. We observed that molecular hydrogen and C‒C bonds are formed after methane dissociates, and then the system undergoes a nonmetal–metal transition coinciding with hydrogen being transformed from the molecular to the atomic state. The C‒C bonds in the system retain covalent character, even at the highest density of 3.0 g/cm3. [ABSTRACT FROM AUTHOR]

Density functional theory has been widely used in quantum mechanical simulations, but the search for a universal exchange-correlation (XC) functional has been elusive. Over the last two decades, machine-learning techniques have been introduced to approximate the XC functional or potential, and recent advances in deep learning have renewed interest in this approach. In this article, we review early efforts to use machine learning to approximate the XC functional, with a focus on the challenge of transferring knowledge from small molecules to larger systems. Recently, the transferability problem has been addressed through the use of quasi-local density-based descriptors, which are rooted in the holographic electron density theorem. We also discuss recent developments using deep-learning techniques that target high-level ab initio molecular energy and electron density for training. These efforts can be unified under a general framework, which will also be discussed from this perspective. Additionally, we explore the use of auxiliary machine-learning models for van der Waals interactions. [ABSTRACT FROM AUTHOR]

Adsorption of toxic substances is an important research field. In this work, the adsorption dynamics of halogenated and methylated benzenes onto hydroxylated silica upon photoexcitation has been investigated theoretically. The intermolecular interaction between the hydroxy (OH) group and the π electron density at the center of the benzene ring was also a major subject. In the ground state, the order of calculated adsorption energy was consistent with the OH⋅⋅⋅C bond strengths (SiO2–MeBe > SiO2–DimeBe > SiO2–BrBe > SiO2–ClBe > SiO2–FBe > SiO2–Be), implying this bond to be the major contributor to the adsorption. Upon photoexcitation to the first excited (S1) state by adsorbing shortwave-ultraviolet (UV), the OH⋅⋅⋅C bonds in each complex were strengthened with only the order of the bond strengths of SiO2–DimeBe and SiO2–MeBe reversed relative to the order in the ground state. In contrast to OH⋅⋅⋅C bonds, the OH⋅⋅⋅π bonds were all indicated to weaken upon photoexcitation. The results showed that the order of OH⋅⋅⋅π bond strengths in the S1 state to be SiO2–FBe > SiO2–BrBe > SiO2–DimeBe > SiO2–Be > SiO2–ClBe > SiO2–MeBe. However, the change in the corresponding adsorption energy was inconsistent with the order of OH⋅⋅⋅C bond strengths in the S1 state, due to the degree of weakening of the OH⋅⋅⋅π bond being greater than the degree of strengthening of the OH⋅⋅⋅C bonds. These changes were concluded to be induced by local excitation for each of the six complexes. This work has presented the photophysical dynamics of an adsorbent before and after photoexcitation. [ABSTRACT FROM AUTHOR]

Intermetallic compounds were applied widely in the fields of automotive and aerospace because of its excellent shape memory effect. In this work, the structural, mechanical, and thermodynamic properties of Ni–Ti intermetallic compounds are studied by first-principle calculation. The results show that Ti, NiTi3, NiTi2, NiTi, Ni4Ti3, Ni3Ti, Ni4Ti, and Ni are stable based on Born stable criterion. On the mechanical aspect, the bulk modulus of Ni–Ti intermetallic compounds increases with the rising electron density. Their ductility is ranked as follows: NiTi3 > Ni4Ti3 > NiTi2 > Ni4Ti > NiTi > Ni3Ti. And when the ratio of Ni and Ti is 3:1, it is the hardest. In addition, the Ni–Ti intermetallic compounds in this work are anisotropy, except NiTi2. On the thermodynamic aspect, the Debye temperature θD, melting point Tm, and minimum thermal conductivity kmin of Ni–Ti intermetallic compounds increase first and then decrease with the rising content of Ni. The θD and kmin of NiTi3 are the minimum among the Ni–Ti ICs mentioned above, and θD of Ni3Ti and kmin of NiTi are both the maximum. The melting point of Ni3Ti is 1940 K, it is the highest temperature. [ABSTRACT FROM AUTHOR]

The temperature coefficient of resistivity (θ T) of carbon-based materials is a critical property that directly determines their electrical response upon thermal impulses. It could have metal- (positive) or semiconductor-like (negative) behavior, depending on the combined temperature dependence of electron density and electron scattering. Its distribution in space is very difficult to measure and is rarely studied. Here, for the first time, we report that carbon-based micro/nanoscale structures have a strong non-uniform spatial distribution of θ T. This distribution is probed by measuring the transient electro-thermal response of the material under extremely localized step laser heating and scanning, which magnifies the local θ T effect in the measured transient voltage evolution. For carbon microfibers (CMFs), after electrical current annealing, θ T varies from negative to positive from the sample end to the center with a magnitude change of >130% over <1 mm. This θ T sign change is confirmed by directly testing smaller segments from different regions of an annealed CMF. For micro-thick carbon nanotube bundles, θ T is found to have a relative change of >125% within a length of ∼2 mm, uncovering strong metallic to semiconductive behavior change in space. Our θ T scanning technique can be readily extended to nm-thick samples with μm scanning resolution to explore the distribution of θ T and provide a deep insight into the local electron conduction. [ABSTRACT FROM AUTHOR]

This paper explores direct density modulation of high-current electron beam emission from an RF cold cathode using optical excitation. We theoretically study the photo-assisted field emission of periodically bunched electron beams of various pulse shapes under the combined excitation of an RF field and an optical field, using an exact quantum model. Both continuous-wave (CW) and pulsed optical fields are considered. The emission current pulse amplitude, pulse width, electron number density per pulse, as well as pulse shape and its harmonic contents are investigated in detail. For CW photon sources in the UV to NIR range (i.e., 200–1200 nm), increasing the optical intensity under an RF bias tends to change the current pulse from a Gaussian to sinusoidal-like shape, thus offering strong flexibility to control the frequency components in beam current emission. Pulsed photon sources combined with an RF field can produce sharp, high-current electron bunches with pulse duration comparable with or even less than that of the optical pulse. A contour map of the density modulation depth is constructed for different combinations of RF and laser fields. The results provide insight into unlocking new opportunities to achieve direct density modulation during electron current emission by optical means. [ABSTRACT FROM AUTHOR]

We demonstrate similarity rules for inductively coupled plasmas with thermohydrodynamic coupling effects using two-dimensional fluid simulations and theoretical analyses of the gas flow and heat transfer equations. The results confirm the validity of conventional similarity laws, e.g., the similarity relation for electron density, which can be violated by the nonlinear gas heating effects from exothermic and endothermic reactions. The nonlinear gas heating can obviously perturb the invariance of spatial distributions of the gas flow velocity, resulting in the electron density decreasing nonproportionally with different scaling factors. Adding an external heat source can mitigate the violation of the gas temperature scaling law, thus maintaining the validity of similarity relations to some extent. In addition, two kinds of scaling relations for excited-state argon atoms are identified with and without the consideration of nonlinear collisions. [ABSTRACT FROM AUTHOR]

One-electron reduced density matrices (1RDMs) from equation-of-motion (EOM) coupled-cluster with single and double excitations (CCSD) calculations are analyzed to assess their N-representability (i.e., whether they are derivable from a physical N-electron state). We identify EOM-CCSD stationary states whose 1RDMs violate either ensemble-state N-representability conditions or pure-state conditions known as generalized Pauli constraints. As such, these 1RDMs do not correspond to any physical N-electron state. Unphysical states are also encountered in the course of time-dependent EOM-CC simulations; when an external field drives transitions between a pair of stationary states with pure-state N-representable 1RDMs, the 1RDM of the time-dependent state can violate ensemble-state conditions. These observations point to potential challenges in interpreting the results of time-dependent EOM-CCSD simulations. [ABSTRACT FROM AUTHOR]

Thermoelectric transport properties of Janus monolayers M2P2S3Se3 (M = Zn and Cd) are investigated by the first-principles based transport theory. The Zn2P2S3Se3 and Cd2P2S3Se3 monolayers are indirect-gap semiconductors. The high polarizability of M-Se/S bonds in the MS3Se3 distorted octahedrons leads to anharmonic phonon behavior, which produces an intrinsic lattice thermal conductivity (κl) as low as 1.06 and 1.99 W m−1 K−1 at 300 K for Zn2P2S3Se3 and Cd2P2S3Se3 monolayers, respectively. The lower κl of the Zn2P2S3Se3 monolayer is mainly attributed to more pronounced flat modes of the phonon dispersion in a frequency range of 1–1.7 THz caused by the softer Zn–Se/S bonds. The polar optical phonon scattering of carriers surprisingly plays a dominant role in carrier transport of both the monolayers, which greatly suppresses the electrical conductivity and thereby the power factor by about an order of magnitude. The predicted figure of merit (zT) increases monotonically with the temperature at the optimal carrier density, and at the operating temperature of 1200 K, it reaches an optimal value of 0.86 at an optimal electron density of ∼ 1.5 × 1 0 13 cm−2 for the n-type Zn2P2S3Se3 monolayer and 0.30 at an optimal electron density of ∼ 7 × 1 0 12 cm−2 for the n-type Cd2P2S3Se3 monolayer. [ABSTRACT FROM AUTHOR]

In this work, we develop an accurate and efficient XGBoost machine learning model for predicting the global-density-dependent range-separation parameter, ωGDD, for long-range corrected functional (LRC)-ωPBE. This ω GDD ML model has been built using a wide range of systems (11 466 complexes, ten different elements, and up to 139 heavy atoms) with fingerprints for the local atomic environment and histograms of distances for the long-range atomic correlation for mapping the quantum mechanical range-separation values. The promising performance on the testing set with 7046 complexes shows a mean absolute error of 0.001 117 a 0 − 1 and only five systems (0.07%) with an absolute error larger than 0.01 a 0 − 1 , which indicates the good transferability of our ω GDD ML model. In addition, the only required input to obtain ω GDD ML is the Cartesian coordinates without electronic structure calculations, thereby enabling rapid predictions. LRC-ωPBE ( ω GDD ML ) is used to predict polarizabilities for a series of oligomers, where polarizabilities are sensitive to the asymptotic density decay and are crucial in a variety of applications, including the calculations of dispersion corrections and refractive index, and surpasses the performance of all other popular density functionals except for the non-tuned LRC-ωPBE. Finally, LRC-ωPBE ( ω GDD ML ) combined with (extended) symmetry-adapted perturbation theory is used in calculating noncovalent interactions to further show that the traditional ab initio system-specific tuning procedure can be bypassed. The present study not only provides an accurate and efficient way to determine the range-separation parameter for LRC-ωPBE but also shows the synergistic benefits of fusing the power of physically inspired density functional LRC-ωPBE and the data-driven ω GDD ML model. [ABSTRACT FROM AUTHOR]

Understanding ultrafast response of a semiconductor is necessary for next-generation optoelectronic device applications. Here, we investigate the ultrafast response of an archetypal semiconductor Ge [111] crystal upon photoexcitation at two pump wavelengths, 800 nm (fundamental) and 400 nm (second harmonic, UV radiation), using time-resolved x-ray diffraction (TXRD). The simulated TXRD profiles using a proposed four-layer model and Takagi–Taupin equations reveal that the strain propagation is primarily due to electron diffusion. Intriguingly, the initial (<100 ps) fast decrease in the induced strain for second harmonic excitation suggests that the strain originates from the deformation potential (DP) effect. The higher photon energy (second harmonic pump) excites the electrons to higher conduction band valleys, resulting in DP-induced strain compared to the fundamental pump, which only generates thermo-elastic strain. The DP strain, estimated from the DP coefficient (simulated via density functional theory-based electronic structure simulations) and electron density (simulated from experimental results), shows an excellent agreement with the observed strain. The strain after ∼100 ps delay for second harmonic excitation and strain from fundamental excitation are attributed to the thermo-elastic effect as confirmed by the density-dependent two-temperature model. Our study reveals the long-lasting DP effect in Ge [111], which provides an opportunity to avoid heating in optoelectronic devices due to the thermo-elastic effect at the initial time scale. [ABSTRACT FROM AUTHOR]

In this work, an analytical hybrid model, which consists of an analytical electromagnetic model and a global model, is developed to investigate the E to H mode transition in a planer inductively coupled plasma. By employing the hybrid model, the effect of discharge frequency, oxygen content, and gas pressure on the E to H mode transition is investigated. The results show that the electron density increases rapidly with coil current when the discharge shifts to the H mode, and the mode transition becomes smoother and occurs at lower current when the driving frequency is higher. As oxygen content increases, the electron density declines, and the threshold current for the mode transition exhibits a rising trend. The evolution of the threshold current with pressure is nonlinear; i.e., it decreases first and then increases, and the minimum value varies with discharge frequency. In addition, the plasma composition also changes during the E to H mode transition; i.e., all the charged species densities increase with coil current, except the O − density, which varies nonlinearly, and this indicates the decreasing electronegativity in the H mode. The results obtained in this work are helpful for understanding the effect of different dischar Ar / O 2 ge parameters on the E to H mode transition in Ar / O 2 inductive discharges. [ABSTRACT FROM AUTHOR]

The comparison of experimentally found absorption limits, and their variations in compound semiconductors, with theoretical expectations was never a particularly studied subject, although absorption limits in semiconductors could be critical to certain optoelectronic device applications. We introduce a model, which accurately fits the distinct absorption saturation parameter linked to the effective electron density of states. [ABSTRACT FROM AUTHOR]

High pressure has been recognized as an important tool in molecule and materials research, and thus, it is expected to be used to understand the evolution of electronic states and geometric structures in superatoms. In this work, by studying three characteristic axial compressions on a typical endohedral metallofullerene superatom U@C28 with Td symmetry, we find that the triplet ground electronic state is preserved when the compression moves along the direction that reduces the symmetry to D2d, but the electronic state of the structure compressed along the direction of symmetry reduction to C2v or Cs is transformed into a singlet. The transition is attributed to the distinction in the response of electron spin to different axial compressions, which results in a change in the electron occupation mode of the system. Furthermore, we also confirm the gradual evolution from stereo to near-plane superatoms and the connection between their electron structures. This is reflected in the fact that the electron density distributions of the superatomic molecular orbitals (SAMOs) with extension along the restricted degrees of freedom ( D z 2 , F z 3 SAMOs) gradually contract, and the delocalization destruction of special orbitals is associated with this freedom. In addition, Raman and ultraviolet–visible spectra show a hyperchromic effect and redshift of characteristic peaks during axial compression, which are expected to be used for fingerprinting the superatomic planarization. Therefore, our work provides new insights based on high pressure for future research toward the discovery of physical properties and applications of superatoms. [ABSTRACT FROM AUTHOR]

We develop a Floquet surface hopping approach to deal with nonadiabatic dynamics of molecules near metal surfaces subjected to time-periodic drivings from strong light–matter interactions. The method is based on a Floquet classical master equation (FCME) derived from a Floquet quantum master equation (FQME), followed by a Wigner transformation to treat nuclear motion classically. We then propose different trajectory surface hopping algorithms to solve the FCME. We find that a Floquet averaged surface hopping with electron density (FaSH-density) algorithm works the best as benchmarked with the FQME, capturing both the fast oscillations due to the driving and the correct steady-state observables. This method will be very useful to study strong light–matter interactions with a manifold of electronic states. [ABSTRACT FROM AUTHOR]

We investigate the source of error in the Thomas–Fermi–von Weizsäcker (TFW) density functional relative to Kohn–Sham density functional theory (DFT). In particular, through numerical studies on a range of materials, for a variety of crystal structures subject to strain and atomic displacements, we find that while the ground state electron density in TFW orbital-free DFT is close to the Kohn–Sham density, the corresponding energy deviates significantly from the Kohn–Sham value. We show that these differences are a consequence of the poor representation of the linear response within the TFW approximation for the electronic kinetic energy, confirming conjectures in the literature. In so doing, we find that the energy computed from a non-self-consistent Kohn–Sham calculation using the TFW electronic ground state density is in very good agreement with that obtained from the fully self-consistent Kohn–Sham solution. [ABSTRACT FROM AUTHOR]

Atmospheric repetitive He discharge with 10 ns current peak width and 3 × 10 11 V/s voltage front rise working in jet geometry is studied. This part deals with the ionization waves, electron density, and electric field dynamics. The electron density (n e) is measured by Stark broadening of the H Balmer β (H β) and He emission lines, the electric field is analyzed using Stark polarization spectroscopy, and the ionization waves are studied by fast imaging. We found that the ionization fronts propagate in the quartz tube with a velocity of about 5 × 10 5 m/s; this velocity slowly decreases along the tube but may jump in the open air at some conditions. In the space between electrodes, n e increases rapidly at the beginning, reaching about 7 × 10 15 cm − 3 , which corresponds to electron avalanche defining the discharge current peak. In the tube, the electrons are concentrated in the ionization wavefronts having low density (< 10 14 cm − 3 ). Before the avalanche, a macroscopic (electrode-induced) electric field dominates between the electrodes peaking at about 8 kV/cm as deduced from H β peak splitting, whereas during the avalanche, H β reveals a double-Lorentzian polarization-insensitive profile imposed by two electron populations. In the low-density electron group, n e does not exceed 10 14 cm − 3 , whereas the high-density group is responsible for the observed electron density peak formation. After a rapid decay of the electrode-induced field, the microscopic electric field (induced by space-charge) dominates, peaking at about 25 kV/cm after the electron density peak. Certain electric field anisotropy is also detected in the quartz tube, confirming the wavefront propagation. [ABSTRACT FROM AUTHOR]

We investigated the effect of the sheath around the probe tips on the transmission spectrum of a cutoff probe using an electromagnetic simulation and a circuit model. Our results show that the width of the sheath can change the transmission spectrum, which can affect the absolute value of the electron density. In a real-world cutoff probe structure, this effect may become apparent in a low-density plasma or when a high bias voltage is applied to the plasma. The key factor is capacitance, which contains the sheath component. In the case of a low-density plasma, the change in the sheath capacitance of the sheath region contributes to the shift in the resonant frequency. For thick sheath widths, at least a 5% discrepancy can occur between the actual plasma frequency and the measurement owing to variations in the capacitance, particularly the sheath components surrounding the probe. We expect that this study will facilitate reduction in the measurement error and uncertainty in microwave cutoff probe measurements, particularly when applied to low-density plasma measurements. [ABSTRACT FROM AUTHOR]

Laser-induced breakdown and subsequent plasma are produced in ambient air in the proximity of an aqueous surface using a Nd:YAG Q-switched laser at 1064 nm with a pulse width of 9 ns and a delivered focused input energy of 170 mJ. The distance between the focal point of a 10 cm convex lens and the aqueous surface is 4 mm with laser propagation perpendicular to the surface. Using an intensified CCD camera attached to a 1-m spectrometer, spatial and wavelength-resolved plasma emission data are obtained for delay times after breakdown ranging from 50 ns to 10 μs with a gate window typically 5 ns. Plasma electron density is determined by applying Lorentzian fitting and FWHM extraction to three Stark-broadened spectral lines: N II 3P-3Do multiplet (593.85 nm), Hα (656.27 nm), and the Na D doublet (589.00 and 589.59 nm). One-dimensional spatially resolved measurements of the total emission intensity and electron density are obtained by binning the camera image along the laser axis in intervals of 250 μm and are reported as a function of time from 50 ns to 10 μs. Two plasmas are ignited from a single laser pulse; one from laser breakdown at the water surface and the other a few nanoseconds later from laser-induced air breakdown at the focal point of 4 mm above the water surface. Comparisons between the evolution of the air plasma near and far from the water surface are presented along with data for the water surface plasma itself. [ABSTRACT FROM AUTHOR]

Electronegative inductively coupled plasmas (ICPs) are used for conductor etching in the microelectronics industry for semiconductor fabrication. Pulsing of the antenna power and bias voltages provides additional control for optimizing plasma–surface interactions. However, pulsed ICPs are susceptible to capacitive-to-inductive mode transitions at the onset of the power pulse due to there being low electron densities at the end of the prior afterglow. The capacitive (E) to inductive (H) mode transition is sensitive to the spatial configuration of the plasma at the end of the prior afterglow, circuit (matchbox) settings, operating conditions, and reactor configurations, including antenna geometry. In this paper, we discuss results from a computational investigation of E–H transitions in pulsed ICPs sustained in Ar/Cl2 and Ar/O2 gas mixtures while varying operating conditions, including gas mixture, pulse repetition frequency, duty cycle of the power pulse, and antenna geometry. Pulsed ICPs sustained in Ar/Cl2 mixtures are prone to significant E–H transitions due to thermal dissociative attachment reactions with Cl2 during the afterglow which reduce pre-pulse electron densities. These abrupt E–H transitions launch electrostatic waves from the formation of a sheath at the boundaries of the plasma and under the antenna in particular. The smoother E–H transitions observed for Ar/O2 mixture results from the higher electron density at the start of the power pulse due to the lack of thermal electron attaching reactions to O2. Ion energy and angular distributions (IEADs) incident onto the wafer and the dielectric window under the antenna are discussed. The shape of the antenna influences the severity of the E–H transition and the IEADs, with antennas having larger surface areas facing the plasma producing larger capacitive coupling. Validation of the model is performed by comparison of computed electron densities with experimental measurements. [ABSTRACT FROM AUTHOR]

The excitation energies, transition rates, collisional-excitation cross sections, and collisional-excitation rate coefficients of N II ions have been calculated by the relativistic configuration-interaction method with the implementation of the flexible atomic code. The population rate coefficients were subsequently investigated and shown that the net population rate coefficients of the 2p3d configuration are greater than those of the 2p3p configuration at an identical electron temperature. A reasonable collisional-radiative model has been constructed to simulate the 2p3s–2p3p and 2p3p–2p3d spectra, which were in reasonable agreement with the lightning data presently obtained in experimental measurements. A further application was implemented in effectively determining the lightning parameters, with the aid of a certain area surrounded by the intersections of contours of multiple line-intensity ratios on the two-dimensional plane of electron temperature and electron density. [ABSTRACT FROM AUTHOR]