Short-range Coulomb Interaction Research Articles

Hierarchical Self-Aggregation of Multifunctional Steviol Glycosides in Aqueous Solutions.

Steviol glycosides (SGs) are a natural sweetener widely used in the food and beverage industry, but the low solubility and stability of SG aqueous solutions greatly limit their application performance, especially in liquid formulations. In this work, we explore the solubility behavior of rebaudioside A (Reb A) in water, a major component of SGs, with the aim of clarifying the underlying mechanisms of the solubility and stability constraints of SGs, as well as the impact on their multifunctional properties. We demonstrate for the first time that Reb A exhibits hierarchical self-assembly in solutions, forming spherical micelles first when the concentration exceeds its critical micelle concentration (5.071 mg/mL), which then further assemble into large rod-like aggregates. The formation of such large Reb A aggregates is mainly dominated by hydrogen bonding and short-range Coulomb interaction energy, thus leading to the low solubility and precipitation of Reb A solutions. Surprisingly, aggregated Reb A structures display significantly improved organoleptic properties, revealing that self-aggregation can be developed as a simple, efficient, and green strategy for improving the taste profile of SGs. Additionally, the self-aggregation of Reb A at high concentrations impairs active encapsulation and also affects its interfacial and emulsifying properties.

Cation-induced changes in the inner- and outer-sphere mechanisms of electrocatalytic CO2 reduction

The underlying mechanism of cation effects on CO2RR remains debated. Herein, we study cation effects by simulating both outer-sphere electron transfer (OS-ET) and inner-sphere electron transfer (IS-ET) pathways during CO2RR via constrained density functional theory molecular dynamics (cDFT-MD) and slow-growth DFT-MD (SG-DFT-MD), respectively. Our results show without any cations, only OS-ET is feasible with a barrier of 1.21 eV. In the presence of K+ (Li+), OS-ET shows a very high barrier of 2.93 eV (4.15 eV) thus being prohibited. However, cations promote CO2 activation through IS-ET with the barrier of only 0.61 eV (K+) and 0.91 eV (Li+), generating the key intermediate (adsorbed CO{}_{2}^{delta -}). Without cations, CO2-to-CO{}_{2}^{delta -}(ads) conversion cannot proceed. Our findings reveal cation effects arise from short-range Coulomb interactions with reaction intermediates. These results disclose that cations modulate the inner- and outer-sphere pathways of CO2RR, offering substantial insights on the cation specificity in the initial CO2RR steps.

Joint probability calculation of the lateral velocity distribution in strong field ionization process

We describe an approach to the description of the time-development of the process of strong field ionization of atoms based on the calculation of the joint probability of occurrence of two events, event B being finding atom in the ionized state after the end of the laser pulse, event A being finding a particular value of a given physical observable at a moment of time inside the laser pulse duration. As an example of such an physical observable we consider lateral velocity component of the electron’s velocity. Our approach allows us to study time-evolution of the lateral velocity distribution for the ionized electron during the interval of the laser pulse duration. We present results of such a study for the cases of target atomic systems with short range Yukawa and Coulomb interactions.

Binding of human serum albumin with uranyl ion at various pH: an all atom molecular dynamics study

Uranium is routinely handled in various stages of nuclear fuel cycle and its association with human serum albumin (HSA) has been reported in literature, however, their binding characteristics still remains obscure. The present study aims to understand interaction of uranium with HSA by employing all atom molecular dynamics simulation of the HSA-metal ion complex. His67, His247 and Asp249 residues constitute the major binding site of HSA, which capture the uranyl ion (UO2 2+). A total of six sets of initial coordinates are used for Zn2+-HSA and UO2 2+-HSA system at pH = 4, 7.4 and 9, respectively. Enhance sampling method, namely, well-tempered meta-dynamics (WT-MtD) is employed to study the binding and un-binding processes of UO2 2+ and Zn2+ ions. Potential of mean force (PMF) profiles are generated for all the six sets of complexes from the converged WT-MtD run. Various basins and barriers are observed along the (un)binding pathways. Hydrogen bond dynamics and short-range Coulomb interactions are evaluated from the equilibrium run at each basins and barriers for both the ions at all pH values. The binding of UO2 2+ ion with HSA is the result of the dynamical balance between UO2 2+-HSA and UO2 2+-water short range Coulomb interactions. Zn2+ ion interact more strongly than UO2 2+ at all pH through short range Coulomb interactions. PMF values further concludes that UO2 2+ cannot associate to the Zn2+ bound HSA protein but can be captured by free HSA at all pH values i.e. endosomal, alkaline and physiological pH. Communicated by Ramaswamy H. Sarma

Viscoelasticity of Low-Molecular-Weight Polyelectrolytes.

Shear-thickening fluids that absorb the impact energy of high-velocity projectiles are of great interest for aerospace and body-armor applications. In such a frame, we investigate transient states of neat and aqueous polyelectrolytes (PE) having low molecular weights and containing poly([2-(methacryloyloxy)ethyl]trimethylammonium) as polycations and poly(acrylamide-co-acrylic acid) as polyanions. We compare results with those of bulk water. We employ nonequilibrium molecular dynamics to simulate oscillatory shear, mainly in the linear viscoelastic regime. We find that neat PE exhibits properties of a viscoelastic solid, whereas water and the aqueous mixture of PE conform to viscoelastic liquids with Maxwellian behavior at low angular frequencies. Terminal relaxation times are ∼0.499 and ∼1.385 ps for water and the aqueous mixture of PE, respectively. At high angular frequencies, storage moduli show anomalous behaviors that correspond to transitions between shear thinning and shear thickening in complex shear viscosities. The change in potential energy with the increase of the angular frequency is mainly driven by intramolecular interactions for neat PE, whereas short-range Coulomb interactions are the major contributions for water and the aqueous mixture of PE. Upon observation of the molecular configurations, only the local polyionic structure in the aqueous mixture of PE shows improvement when increasing the angular frequency, whereas the rest remains barely affected. Thus, the water structure in the aqueous mixture of PE allows the storage of energy elastically through the hydrogen-bond network at large angular frequencies, whereas the mechanical contribution of polyions weakens and fully vanishes at the beginning of shear thinning, explaining the superimposed data with data of bulk water. Our method and findings set the path for future molecular simulations in the nonlinear viscoelastic regime with more complex underlying molecular mechanisms.

Image-Force-Stabilized Interfacial Dipole Layer Impedes Charge Injection Into Disordered Organic Semiconductors

We show using three-dimensional kinetic Monte Carlo simulations that the injection of charge carriers from a metallic electrode into a disordered organic semiconductor is under nominally Ohmic injection conditions strongly impeded by the short-range Coulomb interactions between the charge carriers in the image-force-stabilized interfacial dipole layer. In contrast, master equation and conventional one-dimensional drift-diffusion simulations underestimate these Coulomb interactions due to their mean-field approximation, and are found not to reveal the effect. The simulations predict a reduction of the current density in organic semiconductor devices when the nominal injection barrier is taken very small or even negative, consistent with recent experimental results [Kotadiya et al., Nat. Mater. 17, 329 (2018)]. However, whereas in that work a modification of the energetic disorder near the interface is assumed, we find that the effect is already obtained after including charge-charge interactions beyond a one-dimensional and mean-field approximation.

Toward Laplace MP2 method using range separated Coulomb potential and orbital selective virtuals.

We report the development of a new Laplace MP2 (second-order Møller-Plesset) implementation using a range separated Coulomb potential, partitioned into short- and long-range parts. The implementation heavily relies on the use of sparse matrix algebra, density fitting techniques for the short-range Coulomb interactions, while a Fourier transformation in spherical coordinates is used for the long-range part of the potential. Localized molecular orbitals are employed for the occupied space, whereas orbital specific virtual orbitals associated with localized molecular orbitals are obtained from the exchange matrix associated with specific localized occupied orbitals. The range separated potential is crucial to achieve efficient treatment of the direct term in the MP2, while extensive screening is employed to reduce the expense of the exchange contribution in MP2. The focus of this paper is on controllable accuracy and linear scaling of the data entering the algorithm.

Optical response of laser-driven charge-transfer complex described by Holstein-Hubbard model coupled to heat baths: Hierarchical equations of motion approach.

We investigate the optical response of a charge-transfer complex in a condensed phase driven by an external laser field. Our model includes an instantaneous short-range Coulomb interaction and a local optical vibrational mode described by the Holstein-Hubbard (HH) model. Although characterization of the HH model for a bulk system has typically been conducted using a complex phase diagram, this approach is not sufficient for investigations of dynamical behavior at finite temperature, in particular for studies of nonlinear optical properties, where the time irreversibility of the dynamics that arises from the environment becomes significant. We therefore include heat baths with infinite heat capacity in the model to introduce thermal effects characterized by fluctuation and dissipation to the system dynamics. By reducing the number of degrees of freedom of the heat baths, we derive numerically "exact" hierarchical equations of motion for the reduced density matrix of the HH system. As demonstrations, we calculate the optical response of the system in two- and four-site cases under external electric fields. The results indicate that the effective strength of the system-bath coupling becomes large as the number of sites increases. Excitation of electrons promotes the conductivity when the Coulomb repulsion is equivalent to or dominates the electron-phonon coupling, whereas excitation of optical vibrations always suppresses the conductivity.

Investigating the electronic origins of the repulsion between substitutional and interstitial solutes in hcp Ti

The high solubility of oxygen in Ti, Zr and Hf makes it difficult to stabilize the protective oxide scales on their surfaces as the subsurface regions can serve as boundless sinks that continuously dissolve oxygen. Alloying elements are crucial to reduce the oxygen solubility and diffusivity within early transition metals. Past studies have shown that substitutional alloying additions to titanium repel interstitial oxygen. Here we use first-principles calculations to show that this repulsion is short ranged and identify a variety of factors that are likely responsible for the repulsive interaction. We identify a unique hybridization phenomenon between dissolved substitutional elements and interstitial oxygen within hcp Ti that leads to a repulsive interaction at short distances, similar to that between closed-shell atoms. Calculations of Bader charges also suggest the existence of short-range Coulomb interactions due to the accumulation of charge on the substitutional solute and interstitial oxygen that is drawn from the Ti host.

Intrachain and Interchain Exciton–Exciton Annihilation in Donor–Acceptor Copolymers

PM6 is a donor-acceptor copolymer widely used in high-efficiency organic solar cells (OSC). Here, we report the observation of exciton-exciton annihilation (EEA) in both PM6 copolymer solution and film. We find that the EEA mechanisms are distinct in these two systems. In the PM6 solution, EEA occurs via the long-range dipole-dipole interaction between intrachain excitons, while in the PM6 film it takes place between the interchain polaron pairs (spatially indirect excitons) via the short-range Coulomb interaction. The quantum yield of free polaron formation in the film is also quantified, which indicates that EEA leads to extra interchain polaron-pair dissociation, accounting for the enhanced free polaron formation.

Orbital Chern Insulator and Quantum Phase Diagram of a Kagome Electron System with Half-Filled Flat Bands.

We study the quantum phase diagram of electrons on kagome lattice with half-filled lowest flat bands by considering the antiferromagnetic Heisenberg interaction J, and short-range Coulomb interaction V. In the weak J regime, we identify a fully spin-polarized phase. The presence of finite V drives a spontaneous chiral current, which makes the system an orbital Chern insulator by contributing an orbital magnetization. Such an out-of-plane orbital magnetization allows the presence of a Chern insulating phase independent of the spin orientation in contrast to the spin-orbit coupling induced Chern insulator that disappears with in-plane ferromagnetism constrained by symmetry. Such a symmetry difference provides a criterion to distinguish the physical origin of topological responses in kagome systems. The orbital Chern insulator is robust against small coupling J. By further increasing J, we find that the ferromagnetic topological phase is suppressed, which first becomes partially polarized and then enters a nonmagnetic phase with spin and charge nematicity. The frustrated flat band allows the spin and Coulomb interaction to play an essential role in determining the quantum phases.

Tunable pseudo-magnetic fields for polaritons in strained metasurfaces

Pseudo-magnetic fields generated in artificially strained lattices have enabled the emulation of exotic phenomena once thought to be exclusive to charged particles. However, they have so far failed to emulate the tunability of real magnetic fields because they are determined solely by the engineered strain configuration, rendering them fixed by design. Here, we unveil a universal mechanism to tune pseudo-magnetic fields for polaritons supported by a strained honeycomb metasurface composed of interacting dipole emitters/antennas. Without altering the strain configuration, we show that the pseudo-magnetic field strength can be tuned by modifying the surrounding electromagnetic environment via an enclosing cavity waveguide, which modifies the nature of the dipole–dipole interactions. Owing to the competition between short-range Coulomb interactions and long-range photon-mediated interactions, the pseudo-magnetic field can be entirely switched off at a critical cavity width, without removing the strain. Consequently, by varying only the cavity width, we demonstrate a tunable Lorentz-like force that can be switched on/off and a collapse and revival of polariton Landau levels. Unlocking this tunable pseudo-magnetism poses new intriguing questions beyond the paradigm of conventional tight-binding physics. A method to tune pseudo-magnetic fields for polaritons on a strained metasurface is demonstrated.

Hubbard excitons in two-dimensional nanomaterials

Excitons in two-dimensional nanomaterials are studied by solving the many-electron Hamiltonian with a configuration-interaction approach. It is shown that graphene or phosphorene nanoflakes can not accommodate any excitonic bound states if the long-range Coulomb interaction is suppressed when the systems are placed in a high-k dielectric environment or on a metal substrate. Hence it is revealed that an electron–hole pair created by an optical excitation does not always form an exciton even in a confined nanostructure. The negative exciton binding energy is found to exhibit distinct dependence on the strength of short-range Coulomb interaction as the system undergoes a phase transition from non-magnetic to anti-ferromagnetic. It is further shown that the electron–hole pair may form an exciton state only when the long-range Coulomb interaction is recovered in the nanoflakes.

Simulation of the Impact of Ionized Impurity Scattering on the Total Mobility in Si Nanowire Transistors.

Nanowire transistors (NWTs) are being considered as possible candidates for replacing FinFETs, especially for CMOS scaling beyond the 5-nm node, due to their better electrostatic integrity. Hence, there is an urgent need to develop reliable simulation methods to provide deeper insight into NWTs’ physics and operation, and unlock the devices’ technological potential. One simulation approach that delivers reliable mobility values at low-field near-equilibrium conditions is the combination of the quantum confinement effects with the semi-classical Boltzmann transport equation, solved within the relaxation time approximation adopting the Kubo–Greenwood (KG) formalism, as implemented in this work. We consider the most relevant scattering mechanisms governing intraband and multi-subband transitions in NWTs, including phonon, surface roughness and ionized impurity scattering, whose rates have been calculated directly from the Fermi’s Golden rule. In this paper, we couple multi-slice Poisson–Schrödinger solutions to the KG method to analyze the impact of various scattering mechanisms on the mobility of small diameter nanowire transistors. As demonstrated here, phonon and surface roughness scattering are strong mobility-limiting mechanisms in NWTs. However, scattering from ionized impurities has proved to be another important mobility-limiting mechanism, being mandatory for inclusion when simulating realistic and doped nanostructures, due to the short range Coulomb interaction with the carriers. We also illustrate the impact of the nanowire geometry, highlighting the advantage of using circular over square cross section shapes.

A Necessary Trade-off for Semiclassical Electrodynamics: Accurate Short-Range Coulomb Interactions versus the Enforcement of Causality?

We investigate two key representative semiclassical approaches for propagating resonant energy transfer (RET) between a pair of electronic two-level systems (donor and acceptor) with coupled Maxwell-Liouville equations. On the one hand, when the electromagnetic (EM) field is treated classically and Coulomb interactions are treated quantum-mechanically, we find that a quantum-classical mismatch leads to a violation of causality, i.e., the acceptor can be excited before the retarded EM field arrives. On the other hand, if we invoke a classical intermolecular Coulomb operator, we find that the energy transfer in the near field loses quantitative accuracy compared with Förster theory, even though causality is strictly obeyed. Thus, our work raises a fundamental paradox when choosing a semiclassical electrodynamics algorithm. Namely, which is more important: Accurate short-range interactions or long-range causality? Apparently, one cannot have one's cake and eat it too.

Nonlinear-response properties in a simplified time-dependent density functional theory (sTD-DFT) framework: Evaluation of the first hyperpolarizability.

Recent developments in nonlinear imaging microscopy show the need to implement new theoretical tools, which are able to characterize nonlinear optical properties in an efficient way. For second-harmonic imaging microscopy (SHIM), quantum chemistry could play an important role to design new exogenous dyes with enhanced first hyperpolarizabilities or to characterize the response origin in large endogenous biological systems. Such methods should be able to screen a large number of compounds while reproducing their trends and to treat large systems in reasonable computation times. To fulfill these requirements, we present a new simplified time-dependent density functional theory (sTD-DFT) implementation to evaluate the first hyperpolarizability where the Coulomb and exchange integrals are approximated by short-range damped Coulomb interactions of transition density monopoles. For an ultra-fast computation of the first hyperpolarizability, a tight-binding version (sTD-DFT-xTB) is also proposed. In our implementation, a sTD-DFT calculation is more than 600 time faster with respect to a regular TD-DFT treatment, while the xTB version speeds up the entire calculation further by at least two orders of magnitude. We challenge our implementation on three test cases: typical push-pull π-conjugated compounds, fluorescent proteins, and a collagen model, which were selected to model requirements for SHIM applications.

Effect of structural disorder and Coulomb interactions in the superconductor-insulator transition applied to boron doped diamond

The effect of disorder, both structural (non-diagonal) and on-site (diagonal), is studied through the inhomogeneous Bogoliubov-de Gennes (BdG) theory in narrow-band disordered superconductors with a view towards understanding superconductivity in boron doped diamond (BDD) and boron-doped nanocrystalline diamond (BNCD) films. We employ the attractive Hubbard model within the mean field approximation, including the short-range Coulomb interaction between holes in the narrow acceptor band. We study substitutional boron incorporation in a triangular lattice, with disorder in the form of random potential fluctuations at the boron sites. The role of structural disorder was studied through non-uniform variation of the tight-binding coupling parameter where, following experimental findings, we incorporate the concurrent increase in structural disorder with increasing boron concentration. We illustrate stark differences between the effects of structural and on-site disorder and show that structural disorder has a much greater effect on the density of states, mean pairing amplitude and superfluid density than on-site potential disorder. We show that structural disorder can increase the mean pairing amplitude while the spectral gap in the density of states decreases with states eventually appearing within the spectral gap for high levels of disorder. This study illustrates how the effects of structural disorder can explain some of the features found in superconducting BDD and BNCD films such as a tendency towards saturation of the Tc with boron doping and deviations from the expected BCS theory in the temperature dependence of the pairing amplitude and spectral gap.

Dissipative non-equilibrium Green function methodology to treat short range Coulomb interaction: current through a 1D nanostructure

A methodology describing Coulomb blockade in the non-equilibrium Green function formalism is presented. We carried out ballistic and dissipative simulations through a 1D quantum dot using an Einstein phonon model. Inelastic phonons with different energies have been considered. The methodology incorporates the short-range Coulomb interaction between two electrons through the use of a two-particle Green function. Unlike previous work, the quantum dot has spatial resolution i.e. it is not just parameterized by the energy level and coupling constants of the dot. Our method intends to describe the effect of electron localization while maintaining an open boundary or extended wave function. The formalism conserves the current through the nanostructure. A simple 1D model is used to explain the increase of mobility in semi-crystalline polymers as a function of the electron concentration. The mechanism suggested is based on the lifting of energy levels into the transmission window as a result of the local electron–electron repulsion inside a crystalline domain. The results are aligned with recent experimental findings. Finally, as a proof of concept, we present a simulation of a low temperature resonant structure showing the stability diagram in the Coulomb blockade regime.

Abnormal blueshift of the absorption edge in graphene nanodots.

In a conventional semiconductor, when the dielectric screening effect is suppressed, the exciton binding energy increases and the corresponding excitonic transition would exhibit a redshift in the spectrum. In this work, I study the optical properties of hexagonal graphene nanodots by using a configuration interaction approach and reveal that the edge of the absorption spectrum shows an abnormal blueshift as the environmental dielectric constant ϵr decreases. The two dominant many-body effects in the nanodot: the quasiparticle and excitonic effects are both found to scale almost linearly with ϵr-1. The former is shown to have a larger proportionality constant and thus accounts for the blueshift of the absorption edge. In contrast to the long-range Coulomb interaction, the on-site Coulomb energy is found to have a negative impact on the bright excitonic states. In the presence of a strong dielectric screening effect, a strong short-range Coulomb interaction is revealed to be responsible for the disintegration of the bright exciton.

The system of mobile ions in lattice models: Screening effects, thermodynamic and electrophysical properties

The lattice fluid model of the system with short range and long range Coulomb interactions is suggested. In the framework of the collective variables method, the screening of the Coulomb interactions in the bulk is considered. It is shown that the Debye length includes additional concentration dependence inversely proportional to the square root of the mean concentration of vacant sites like what was known at the plane boundary. The Coulomb interaction contribution to the free energy of the system is calculated in the approach close to the mean spherical approximation and is given in an analytical form.The influence of the variation of the crystal field near the system boundary on the structure and characteristics of the electric double layer is investigated. As compared to the system with equal crystal potentials at the lattice sites throughout the system the pronounced difference for the electrical capacitance appears at low absolute values of the surface potential and it is more pronounced for negative electric potentials. The capacitance diverges as the potential values at which the electric field tends to zero and attains negative values in regions of the surface potentials depending on their polarity and values of the surface crystal potential. Negative values of the capacitance may indicate the thermodynamic instability of the system that can result from neglecting the short range interaction contribution.