Long-range Coulomb Forces Research Articles

Madelung Strain in Cuprate Superconductors – A Route to Enhancement of the Critical Temperature

“Madelung Strain” in cuprate films containing metal (M = La1.56Sr0.44CuO4) and insulator (I = La2CuO4) layers: X-ray diffraction shows that, unexpectedly, the volume of unit cell of the top layer adjusts to that of the bottom layer. The effect is due to long-range Coulomb forces; it affects interfacial superconductivity because the critical temperature scales with the unit-cell height.

Low-temperature fluid-phase behavior of ST2 water

We perform histogram-reweighting Monte Carlo simulations of the ST2 model of water in the grand-canonical ensemble in order to investigate its low-temperature fluid-phase behavior. Using Ewald summation treatment of long-range electrostatic interactions, we locate the critical point of the liquid-liquid transition at T=237±4 K, ρ=0.99±0.02 g/cc, P=167±24 MPa. Contrary to previous reports in the literature [Brovchenko et al., J. Chem. Phys. 118, 9473 (2003); Brovchenko et al., J. Chem. Phys. 123, 044515 (2005)], according to which there are three liquid-liquid transitions in ST2 with simple truncation of electrostatic interactions, and two in ST2 with reaction field treatment of long-range Coulombic forces, we find only one liquid-liquid transition. Our work points to the sensitivity of results to the proper treatment of electrostatic interactions, and to the introduction of artificial constraints that limit the magnitude of density fluctuations.

Scaling and self-organized criticality in proteins II

The complexity of proteins is substantially simplified by regarding them as archetypical examples of self-organized criticality (SOC). To test this idea and to elaborate it, this article applies the Moret-Zebende (MZ) SOC hydrophobicity scale to transport repeat proteins of the HEAT superfamily, importin beta, and transportin, as well as the export protein Cse1p, and their ubiquitous cargo manager Ran. The difference between the MZ scale and conventional hydrophobicity scales reflects long-range conformational forces that are central to protein functionality. These compete with long-range Coulomb forces associated with cationic and anionic side chains in a revealing way.

General time-independent theory of ionization and breakup reactions

A rigorous formulation of non-relativistic time-dependent multiparticle collision theory was developed some time ago, in which the effect of long-range Coulomb forces was accounted for by a modification of the standard wave operator that appears in treatments of neutral-particle scattering. This theory is here converted to a time-independent form, with the wave-operator modification replaced by the use of Coulomb-modified plane waves in the construction of the wave packets that appear in the theory. This provides a convenient basis for the development of approximation techniques in configuration space, including the use of variational methods of calculation, based on integral identities for the transition amplitudes. In many cases oscillatory divergences appear in the integrals representing the ionization or breakup amplitudes. A method for removing such divergences by an averaging of the integrand at great distances is defined.

Comparative investigations of the P– V– T relationship of NaCl at high pressure and temperature

Two different potential models of molecular dynamics (MD) simulations have been applied to investigate the pressure–volume–temperature ( P– V– T) relationship and lattice parameter of NaCl under high pressure and temperature. The first one is the shell model (SM) potentials in which due to the short-range interaction pairs of ions are moved together as is the case in polarization of a crystal due to the motion of the positive and negative ions, and the second one is the two-body rigid-ion Born–Mayer–Huggins–Fumi–Tosi (BMHFT) potentials with full treatment of long-range Coulomb forces. The P– V relationship at 300 K, T– V relationship at zero pressure, and lattice parameter a, have been obtained and compared with the available experimental data and other theoretical results. Compared with SM potentials, the MD simulation with BMHFT potentials is very successful in reproducing accurately the measured volumes of NaCl. At an extended pressure and temperature ranges, P– V relationship under different isotherms at selected temperatures, T– V relationship under different pressures, and lattice parameter a have also been predicted. The properties of NaCl are summarized in the pressure range 0–30 GPa and the temperature up to 2000 K.

The one-dimensional Wigner crystal in carbon nanotubes

A dilute system of electrons interacting through long-range Coulomb forces has been predicted to form a periodic solid known as a Wigner crystal. To date, this state has been observed directly only in two-dimensional systems. Here, using low-temperature single-electron transport spectroscopy, we show that the hole gas in low-disorder semiconducting carbon nanotubes forms a one-dimensional Wigner crystal. In an axial magnetic field, we observe three distinct regimes of spin and isospin polarization as carrier density is varied. We explain these regimes in terms of a Wigner crystal picture based on a gapped Luttinger liquid model, with the carriers represented by spatially localized solitons. Our observations could enable greater control over the behaviour of the spatially separated system of carriers. Such control, combined with the inherently long coherence times of carriers in carbon nanotubes, could prove useful in the development of solid-state quantum computing. The one-dimensional case of the so-called ‘Wigner crystal’ phase of electrons—long predicted but previously only seen in two-dimensional electron systems—has finally been observed, in a carbon nanotube.

Hydrodynamic model for relaxation of optically injected currents in quantum wells

We use a hydrodynamic model to describe the relaxation of optically injected currents in quantum wells on a picosecond time scale, numerically solving the continuity and velocity evolution equations with the Hermite-Gaussian functions employed as a basis. The interplay of the long-range Coulomb forces and nonlinearity in the equations of motion leads to rather complex patterns of the calculated charge and current densities. We find that the time dependence of even the first moment of the electron density is sensitive to this complex evolution.

Phonons and electron-phonon interactions in rare-gas crystals at high pressures

The lattice dynamics of compressed rare-gas crystals is theoretically investigated within the ab initio approach in the framework of the Tolpygo model, which explicitly allows for the deformation of electron shells. The deformation of the electron shells is associated with the retardation of the electron response and treated as a nonadiabaticity (the electron-phonon interaction). This approach and the ab initio short-range repulsive potentials are used to construct the dynamic matrix, which makes it possible to calculate the phonon frequencies and the electron-phonon interaction of crystals in the series Ne-Xe at any point of the Brillouin zone. The contributions of the long-range Coulomb and van der Waals forces to the dynamic matrix are the structure sums that depend only on the lattice type. The structure sums for the face-centered cubic lattice are calculated using the Ewald and Emersleben methods, as well as the direct summation over the vectors of the face-centered cubic lattice. The use of 20 spheres in the last case provides an accuracy of no less than four significant figures. An analysis of the role played by the phonon-electron interaction at five points of high symmetry in the Brillouin zone (X, L, U, K, W) at high pressures demonstrates that not only the longitudinal phonon modes (at the points X and L) but also the transverse phonon modes (at the points U, K, and W) are softened. The inclusion of the electron-phonon interaction at the point X improves agreement between the theoretical and experimental phonon frequencies for the argon crystal.

Deciphering the Role of Hydrogen Bonding in Enhancing pDNA−Polycation Interactions

There is considerable interest in the binding and condensation of DNA with polycations to form polyplexes because of their possible application to cellular nucleic acid delivery. This work focuses on studying the binding of plasmid DNA (pDNA) with a series of poly(glycoamidoamine)s (PGAAs) that have previously been shown to deliver pDNA in vitro in an efficient and nontoxic manner. Herein, we examine the PGAA-pDNA binding energetics, binding-linked protonation, and electrostatic contribution to the free energy with isothermal titration calorimetry (ITC). The size and charge of the polyplexes at various ITC injection points were then investigated by light scattering and zeta-potential measurements to provide comprehensive insight into the formation of these polyplexes. An analysis of the calorimetric data revealed a three-step process consisting of two different endothermic contributions followed by the condensation/aggregation of polyplexes. The strength of binding and the point of charge neutralization were found to be dependent upon the hydroxyl stereochemistry of the carbohydrate moiety within each polymer repeat unit. Circular dichroism spectra reveal that the PGAAs induce pDNA secondary structure changes upon binding, which suggest a direct interaction between the polymers and the DNA base pairs. Infrared spectroscopy experiments confirmed both base pair and phosphate group interactions and, more specifically, showed that the stronger-binding PGAAs had more pronounced interactions at both sites. Thus, we conclude that the mechanism of poly(glycoamidoamine)-pDNA binding is most likely a combination of electrostatics and hydrogen bonding in which long-range Coulombic forces initiate the attraction and hydroxyl groups in the carbohydrate comonomer, depending on their stereochemistry, further enhance the association through hydrogen bonding to the DNA base pairs.

Azimuthal angle dependence of Coulomb and nuclear interactions between two deformed nuclei

The azimuthal angle ({phi}) variation of the Coulomb and nuclear heavy ion (HI) potentials is studied in the framework of the double folding model, which is derived from realistic nuclear density distributions and a nucleon-nucleon (NN) interaction. The present calculation shows that the variation of HI potentials with the azimuthal angle depends strongly on the range of the NN forces. For the long-range Coulomb force, the maximum variation with {phi} is about 0.9%, and for HI potential derived from zero-range NN interaction the {phi}-variation can reach up to 90.0%. Our calculations are compared with the recent {phi}-dependence of the HI potential derived from proximity method. The present realistic {phi}-dependence calculations of the HI potential is completely different from the results of the proximity calculations.

Anomalous thermodynamics and phase transitions in neutron star matter

The presence of the long-range Coulomb force in dense stellar matter implies that the total charge cannot be associated with a chemical potential, even if it is a conserved quantity. As a consequence, the analytical properties of the partition sum are modified, changing the order of the phase transitions and affecting the possible occurrence of critical behaviors. The peculiar thermodynamic properties of this system can be understood introducing a model Hamiltonian where each charge is independently neutralized by a uniform background of opposite charge. Some consequences on the characteristics of mixed-phase structures in neutron star crusts and supernova cores are discussed.

The assessment of microscopic charging effects induced by focused electron and ion beam irradiation of dielectrics

Energetic beams of electrons and ions are widely used to probe the microscopic properties of materials. Irradiation with charged beams in scanning electron microscopes (SEM) and focused ion beam (FIB) systems may result in the trapping of charge at irradiation induced or pre-existing defects within the implanted microvolume of the dielectric material. The significant perturbing influence on dielectric materials of both electron and (Ga(+)) ion beam irradiation is assessed using scanning probe microscopy (SPM) techniques. Kelvin Probe Microscopy (KPM) is an advanced SPM technique in which long-range Coulomb forces between a conductive atomic force probe and the silicon dioxide specimen enable the potential at the specimen surface to be characterized with high spatial resolution. KPM reveals characteristic significant localized potentials in both electron and ion implanted dielectrics. The potentials are observed despite charge mitigation strategies including prior coating of the dielectric specimen with a layer of thin grounded conductive material. Both electron- and ion-induced charging effects are influenced by a delicate balance of a number of different dynamic processes including charge-trapping and secondary electron emission. In the case of ion beam induced charging, the additional influence of ion implantation and nonstoichiometric sputtering from compounds is also important. The presence of a localized potential will result in the electromigration of mobile charged defect species within the irradiated volume of the dielectric specimen. This electromigration may result in local modification of the chemical composition of the irradiated dielectric. The implications of charging induced effects must be considered during the microanalysis and processing of dielectric materials using electron and ion beam techniques.

Direct Measurement of Interaction Forces Between Islands on Freely Suspended Smectic C Films Using Multiple Optical Tweezers

Smectic liquid crystals can be made to form freely suspended films, two-dimensional systems locally quantized in thickness by an integral number of smectic layers, on which islands, circular regions of greater thickness than the surrounding film area, can be generated. In smectic C films, each such island is accompanied by a topological defect pair, an s = +1 topological defect inside and an s = −1 defect nearby on the background film. The distortions of the in-plane orientational order of the smectic C director field result in elastic interactions between the islands, with a short-range repulsion and a long-range dipolar attraction governing their stability and leading to their organization in chain-like structures with an equilibrium island separation. We demonstrated previously that such islands can be manipulated using optical tweezers. Using an acousto-optically scanned infrared laser system to generate dynamically controllable, multiple optical traps, we have now directly measured the repulsive and attractive elastic interaction forces between smectic C* islands and have compared the results quantitatively with theory. We find that the interactions between islands are much smaller in the racemic smectic C case than in the chiral smectic C*, an effect we attribute to long-range coulombic forces arising from polarization charges.

Evidence of the Coulomb-force effects in the cross-sections of the deuteron–proton breakup at 130 MeV

High precision cross-section data of the deuteron-proton breakup reaction at 130 MeV deuteron energy are compared with the theoretical predictions obtained with a coupled-channel extension of the CD Bonn potential with virtual Delta-isobar excitation, without and with inclusion of the long-range Coulomb force. The Coulomb effect is studied on the basis of the cross-section data set, extended in this work to about 1500 data points by including breakup geometries characterized by small polar angles of the two protons. The experimental data clearly prefer predictions obtained with the Coulomb interaction included. The strongest effects are observed in regions in which the relative energy of the two protons is the smallest.

Apparent mean-field criticality of liquid–liquid phase transitions in ionic solutions

It is now common knowledge that the critical properties of phase transitions of fluids and fluid mixtures agree with that of the 3 d-Ising model. This statement is proved by phase transitions driven by short-range r −n interactions ( n > 3.97). It was suspected that the universal validity of the 3 d-Ising model may not apply in phase transitions driven by long-range Coulomb forces. In support of this conjecture mean-field critical behaviour has been reported repeatedly for the liquid–liquid phase transition in ionic solutions. However, later work did not state those work, but led to the conclusion that systems with phase transitions driven by Coulomb interactions also belong to the 3 d-Ising universality class. In order to pinpoint the traps that led to false conclusions we review the controversy work on Pitzer's system n-hexyl-triethylammonium n-hexyl-triethylborate/biphenyl ether, on the ternary mixtures of 3-methylpyridine (3MP)/H 20/NaBr and report first results on the solution of the Room Temperature Ionic Liquid (RTIL) 3-hexyl-1-methyl imidazolium tetrafluoroborate in pentanol.

Fate of the Wigner crystal on the square lattice

The phase diagram of a system of electrons hopping on a square lattice and interacting through long-range Coulomb forces is studied as a function of density and interaction strength. The presence of a lattice strongly enhances the stability of the Wigner crystal phase as compared to the case of the two-dimensional electron gas.

Physics of solid and liquid alkali halide surfaces near the melting point

This paper presents a broad theoretical and simulation study of the high-temperature behavior of crystalline alkali halide surfaces typified by NaCl(100), of the liquid NaCl surface near freezing, and of the very unusual partial wetting of the solid surface by the melt. Simulations are conducted using two-body rigid-ion Born-Mayer-Huggins-Fumi-Tosi (BMHFT) potentials, with full treatment of long-range Coulomb forces. After a preliminary check of the description of bulk NaCl provided by these potentials, which seems generally good even at the melting point, we carry out a new investigation of solid and liquid surfaces. Solid NaCl(100) is found in this model to be very anharmonic and yet exceptionally stable when hot. It is predicted by a thermodynamic integration calculation of the surface free energy that NaCl(100) should be a well-ordered, nonmelting surface, metastable even well above the melting point. By contrast, the simulated liquid NaCl surface is found to exhibit large thermal fluctuations and no layering order. In spite of that, it is shown to possess a relatively large surface free energy. The latter is traced to a surface entropy deficit, reflecting some kind of surface short-range order. We show that the surface short-range order is most likely caused by the continuous transition of the bulk ionic melt into the vapor, made of NaCl molecules and dimers rather than of single ions. Finally, the solid-liquid interface free energy is derived through Young's equation from direct simulation of partial wetting of NaCl(100) by a liquid droplet. The resulting interface free energy is large, in line with the conspicuous solid-liquid 27% density difference. A partial wetting angle near 50 degrees close to the experimental value of 48 degrees is obtained in the process. It is concluded that three elements, namely, the exceptional anharmonic stability of the solid (100) surface, the molecular short-range order at the liquid surface, and the costly solid-liquid interface, all conspire to cause the anomalously poor wetting of the (100) surface by its own melt in the BMHFT model of NaCl-and most likely also in real alkali halide surfaces.

Fragmentation channels of large multicharged clusters

We address unifying features of fragmentation channels driven by long-range Coulomb or pseudo-Coulomb forces in clusters, nuclei, droplets, and optical molasses. We studied the energetics, fragmentation patterns, and dynamics of multicharged (A+)n (n=55, 135, 321) clusters. In Morse clusters the variation of the range of the pair-potential induced changes in the cluster surface energy and in the fissibility parameter X=E(Coulomb)2E(surface). X was varied in the range of X=1-8 for short-range interactions and of X=0.1-1.0 for long-range interactions. Metastable cluster configurations were prepared by vertical ionization of the neutral clusters and by subsequent structural equilibration. The energetics of these metastable ionic clusters was described in terms of the liquid drop model, with the coefficients of the volume and surface energies depending linearly on the Morse band dissociation energy. Molecular-dynamics simulations established two distinct fragmentation patterns of multicharged clusters that involve cluster fission into a small number of large, multicharged clusters for X<1 and Coulomb explosion into a large number of individual ions and small ionic fragments for X>1. The Rayleigh instability limit X=1 separates between spatially anisotropic fission and spatially isotropic Coulomb explosion. Distinct features of the fragmentation energetics and dynamics were unveiled. For fission of n=55 clusters, large kinetic and internal energies of the large fragments are exhibited and the characteristic fragmentation time is approximately 700 fs, while for Coulomb explosion the major energy content of the small fragments involves kinetic energy and the characteristic fragmentation time of approximately 300 fs is shorter. The Rayleigh (X=1) limit, leading to isotropic Coulomb explosion, is transcended by a marked enhancement of the Coulomb energy, which is realized for extremely ionized clusters in ultraintense laser fields, or by a dramatic reduction of the surface energy as is the case for the expansion of optical molasses.

Nonperiodic boundary conditions for solvated systems

The simulation of charged and/or strongly polar solutes represents a challenge for standard molecular-dynamics techniques. The use of periodic boundary conditions (PBCs) leads to artifacts due to the interaction between two replicas in the presence of the long-range Coulomb forces. A way to avoid these problems is the use of nonperiodic boundary conditions. A possible realization is to consider a finite system, a sphere, embedded in a reaction field described by the method of the images. In the present work the modified image approximation has been implemented in a molecular-dynamics code and optimized for the use of two standard solvents, water and acetonitrile. The methodology has then been applied to investigate the conformational changes in water-solvated alanine dipeptide. The free-energy surface calculated with this method is comparable to that obtained with PBC.

Kelvin Probe Microscopy of Localized Electric Potentials Induced in Insulating Materials by Electron Irradiation

Kelvin probe microscopy (KPM) is a specialized atomic force microscopy technique in which long-range Coulomb forces between a conductive atomic force probe and a specimen enable the electrical potential at the surface of a specimen to be characterized with high spatial resolution. KPM has been used to characterize nonconductive materials following their exposure to stationary electron beam irradiation in a scanning electron microscope (SEM). Charged beam irradiation of poorly conducting materials results in the trapping of charge at either preexisting or irradiation-induced defects. The reproducible characteristic surface potentials associated with the trapped charge have been mapped using KPM. Potential profiles are calculated and compared with observed potential profiles giving insight into the charging processes and residual trapped charge distributions.