A paramagnetic molecular voltmeter

We have developed a general electron paramagnetic resonance (EPR) method to measure electrostatic potential at spin labels on proteins to millivolt accuracy. Electrostatic potential is fundamental to energy-transducing proteins like myosin, because molecular energy storage and retrieval is primarily electrostatic. Quantitative analysis of protein electrostatics demands a site-specific spectroscopic method sensitive to millivolt changes. Previous electrostatic potential studies on macromolecules fell short in sensitivity, accuracy and/or specificity. Our approach uses fast-relaxing charged and neutral paramagnetic relaxation agents (PRAs) to increase nitroxide spin label relaxation rate solely through collisional spin exchange. These PRAs were calibrated in experiments on small nitroxides of known structure and charge to account for differences in their relaxation efficiency. Nitroxide longitudinal (R(1)) and transverse (R(2)) relaxation rates were separated by applying lineshape analysis to progressive saturation spectra. The ratio of measured R(1) increases for each pair of charged and neutral PRAs measures the shift in local PRA concentration due to electrostatic potential. Voltage at the spin label is then calculated using the Boltzmann equation. Measured voltages for two small charged nitroxides agree with Debye-Hückel calculations. Voltage for spin-labeled myosin fragment S1 also agrees with calculation based on the pK shift of the reacted cysteine.     

Magneto-electronic properties and spin-resolved I–V curves of a Co/GeSe heterojunction diode: an ab initio study

We present ab initio calculations of magnetoelectronic and transport properties of the interface of hcp Cobalt (001) and the intrinsic narrow-gap semiconductor germanium selenide (GeSe). Using a norm-conserving pseudopotentials scheme within DFT, we first model the interface with a supercell approach and focus on the spin-resolved densities of states and the magnetic moment (spin and orbital components) at the different atomic layers that form the device. We also report a series of cuts (perpendicular to the plane of the heterojunction) of the electronic and spin densities showing a slight magnetization of the first layers of the semiconductor. Finally, we model the device with a different scheme: using semiinfinite electrodes connected to the heterojunction. These latter calculations are based upon a nonequilibrium Green’s function approach that allows us to explore the spin-resolved electronic transport under a bias voltage (spin-resolved I–V curves), revealing features of potential applicability in spintronics.     

Based on charge-transfer interaction organic light-response materials: From sphere-like nanoparticles to fibers

We employed a potent and versatile ionic self-assembly (ISA) to prepare stimuli-responsive supramolecular materials using charged surfactants, N-dodecyl-4-(1-methylpip-erazine)-1,8-naphthalimide iodine [C₁₂ndi]I and oppositely charged small molecule, 4-(phenylazo)benzoic acid sodium (PBAS). By transmission electron microscopy, nanospheres could be observed to transform into nanofibers upon irradiated with UV light (365 nm) for 1 h. The UV–vis absorption spectra and fluorescence spectra of the fibers indicate that charge-transfer interaction is regarded as the driving force for the formation of fibers. Density functional theory (DFT) calculations prove that the π–π stacking and electrostatic interactions between [C₁₂ndi]I and PBAS contributes significantly to the resulting aggregates. The supramolecular fibers have the potential applications in some fields, e.g. drug delivery and electro-optical devices.     

Quasiparticle excitations and charge transition levels of oxygen vacancies in hafnia

We calculate the quasiparticle defect states and charge transition levels (CTLs) of oxygen vacancies in monoclinic hafnia using density functional theory (DFT) and the GW method. We introduce the criterion that the quality and reliability of CTLs may be evaluated by calculating the same CTL via two physical paths and show that it is necessary to include important electrostatic corrections previously neglected within the supercell DFT + GW approach. Contrary to previous reports, the oxygen vacancies in hafnia are large positive U centers, where U is the defect charging energy.     

Electrostatically driven spatial patterns in lipid membrane composition

To explore the physical mechanisms that can guide spatial organization at biological membranes, we have constructed simple, cell-free intermembrane junctions. We find that the mechanically driven patterning of proteins uncovered in our earlier work can electrostatically generate spatial patterns in the distribution of charged membrane lipids. Tuning the magnitude of the interaction as a function of composition and ionic strength, and analyzing the interplay between thermodynamics and electrostatics via a Poisson-Boltzmann approach, we are able to determine the charge density and surface potential of the junction components. Surprisingly, the electrostatic potential of the proteins is a minor factor in the lipid reorganization; the protein size and its modulation of the junction topography play the dominant role in driving the electrostatic patterns.     

Spin-polarized two-dimensional electron gas at oxide interfaces

The possibility of formation of a fully spin-polarized 2D electron gas at the SrMnO_3/(LaMnO_3)_1/SrMnO_3 heterostructure is predicted from density-functional calculations. The La(d) electrons become confined in the direction normal to the interface in the electrostatic potential well of the positively charged layer of La atoms, acting as electron donors. These electrons mediate a ferromagnetic alignment of the Mn t_2g spins near the interface via Zener double exchange and become, in turn, spin-polarized due to the internal magnetic fields of the Mn moments.     

Interaction of a dielectric macroparticle with a point charge in plasma

The electrostatic interaction of a charged spherical dielectric macroparticle with a point charge in a plasma in the presence of an external uniform electric field is considered. The electrostatic force and the torque acting on the macroparticle have been determined, and the form of the interaction potential has been established for a nonuniform distribution of free charge on the macroparticle surface. A simple (for calculations) expression for the interaction potential that describes well the exact potential at all interparticle distances is proposed. The angular velocity of the spinning of dust particles caused by a nonuniform distribution of free charge over their surface has been estimated.     

Charge distribution and stability of charged carbon nanotubes

Density-functional calculations of charge distribution on negatively and positively charged nanotubes result in charge density profiles characterized by a significant increase of charge density at the tube ends. These results are in quantitative agreement with classical electrostatic analysis, which assumes constant electrostatic potential on the conductive tube surface. At high charging levels, the tube ends are observed to be unstable due to Coulomb repulsion. By combining ab initio calculations with classical electrostatics, we determine, as a function of tube length and geometry of the tube end, the critical voltage beyond which nanotubes are unstable.     

Computing surface dipoles and potentials of self-assembled monolayers from first principles

We discuss methodological aspects of first principles calculations of surface dipoles and potentials in general, and surface-adsorbed self-assembled monolayers in particular, using density functional theory with a slab/super-cell approach. We show that calculations involving asymmetric slabs may yield highly erroneous results for the surface dipole and demonstrated the efficacy of a simple dipole correction scheme. We explain the importance of the electrostatic dipole distribution, show how to compute it, and establish conditions for the equivalence of calculations for the dipole distribution and the electrostatic potential distribution.     

Self-consistent scattering theoretical method for surfaces: Application to Si(100)

We have developed a method for solving self-consistently the Green's-function equations describing a semiinfinite crystal within local density functional formalism. Based on scattering theory, it yields the potential, charge density, wavevector-resolved layer state densities and the energy spectrum of the surface. A detailed study of the ideal Si(100) surface illustrates the approach and sheds light on differences in previous self-consistent results of matching and supercell calculations for this very surface.     

Ab-initio calculations of electronic structure and optical properties of TiAl alloy

The electronic structures and optical properties of TiAl intermetallic alloy system are studied by the first-principle orthogonalized linear combination of atomic orbitals method. Results on the band structure, total and partial density of states, localization index, effective atomic charges, and optical conductivity are presented and discussed in detail. Total density of states spectra reveal that (near the Fermi level) the majority of the contribution is from Ti-3d states. The effective charge calculations show an average charge transfer of 0.52 electrons from Ti to Al in primitive cell calculations of TiAl alloy. On the other hand, calculations using supercell approach reveal an average charge transfer of 0.48 electrons from Ti to Al. The localization index calculations, of primitive cell as well as of supercell, show the presence of relatively localized states even above the Fermi level for this alloy. The calculated optical conductivity spectra of TiAl alloy are rich in structures, showing the highest peak at 5.73 eV for supercell calculations. Calculations of the imaginary part of the linear dielectric function show a prominent peak at 5.71 eV and a plateau in the range 1.1-3.5 eV.     

Comparison between various finite-size supercell correction schemes for charged defect calculations

We present a comparison of the most common finite-size supercell correction schemes for charged defects in density functional theory calculations. Considered schemes include those proposed by Makov and Payne (MP), Lany and Zunger (LZ), and Freysoldt, Neugebauer, and Van de Walle (FNV). The role of the potential alignment is also assessed. Supercells of various sizes are considered and the corrected formation energies are compared to the values obtained by extrapolation to large supercells. For defects with localized charge distributions, we generally find that the FNV scheme slightly improves upon the LZ one, while the MP scheme generally overcorrects except for point-charge-like defects. We also encountered more complex situations in which the extrapolated values do not coincide. Inspection of the defect electronic structure indicates that this occurs when the defect Kohn–Sham states are degenerate with band-edge states of the host.     

Coupling reducing k-points for photonic crystal fiber calculations

When describing localized electromagnetic modes in dielectric waveguides by the planewave method, a supercell geometry must necessarily be adopted. We demonstrate in the present work that the convergence of the calculations with respect to supercell size depends strongly on the choice of the transverse Bloch wave vector, k. We describe a method to derive k-points that minimize the coupling between repeated images of the guided modes in real space. Calculations have been done for a quadratic and a triangular photonic crystal fiber structure. With the new coupling reducing (CR) k-points, the convergence of the eigenfrequencies for both the fundamental and second order modes with respect to supercell size is considerably improved. The general approach outlined may also be applied in the case of three-dimensional photonic crystal structures.     

Concise presentation of the Coulomb electrostatic potential of a uniformly charged cube

We use a novel method to calculate in closed form the Coulomb electrostatic potential created by a uniformly charged cube at an arbitrary point in space. We apply a suitable transformation of variables that allows us to obtain a simple presentation of the electrostatic potential in one-dimensional integral form. The final concise closed form expression of the Coulomb electrostatic potential of the uniformly charged cube is obtained after completing the calculation of the resulting one-dimensional integrals. Such integrals consist of combinations of products of error functions and power functions that can be solved exactly despite their intimidating appearance. The exact analytic formula for the Coulomb electrostatic potential that we derive reflects the symmetry of the cube and is easy to implement. We illustrate its use by calculating the exact values of the electrostatic potential at some points of symmetry such as the center of cube, center of face of cube, center of edge of cube and corner of cube.     

Wake potential with mobile positive/negative ions in multicomponent dusty plasmas

We employ the test charge approach to calculate the electrostatic potential for a test charge in a multicomponent dusty plasma, whose constituents are the Boltzmann distributed electrons, mobile positive and negative ions, and immobile positive/negative charged dust particles. By using the modified dielectric constant of the dust-ion-acoustic (DIA) waves, the Debye screening and wake potentials are obtained. It is found that the presence of mobile negative ions significantly modify the DIA speed and the wake potential. The present results are relevant to polar mesosphere and microelectronic in the context of charged particle attraction and repulsion.     

Semi-analytical method of calculating the electrostatic interaction of colloidal solutions

We present a semi-analytical method of calculating the electrostatic interaction of colloid solutions for confined and unconfined systems. We expand the electrostatic potential of the system in terms of some basis functions such as spherical harmonic function and cylinder function. The expansion coefficients can be obtained by solving the equations of the boundary conditions, combining an analytical translation transform of the coordinates and a numerical multipoint collection method. The precise electrostatic potential and the interaction energy are then obtained automatically. The method is available not only for the uniformly charged colloids but also for nonuniformly charged ones. We have successfully applied it to unconfined diluted colloid system and some confined systems such as the long cylinder wall confinement, the air–water interfacial confinement and porous membrane confinement. The consistence checks of our calculations with some known analytical cases have been made for all our applications. In theory, the method is applicable to any dilute colloid solutions with an arbitrary distribution of the surface charge on the colloidal particle under a regular solid confinement, such as spherical cavity confinement and lamellar confinement.     

Beam cooling by frictional forces: Monte Carlo calculations and design studies

The design of a device for cooling a beam of very low-energetic charged particles by moderation in matter and simultaneous acceleration in an electrostatic field has been studied both by closed form and Monte Carlo calculations. These calculations show that an increase in spectral density of roughly a factor of 7 can be obtained.     

Spin relaxation measurements of electrostatic bias in intermolecular exploration

We utilize the paramagnetic contribution to proton spin-lattice relaxation rate constants induced by freely diffusing charged paramagnetic centers to investigate the effect of charge on the intermolecular exploration of a protein by the small molecule. The proton NMR spectrum provided 255 resolved resonances that report how the explorer molecule local concentration varies with position on the surface. The measurements integrate over local dielectric constant variations, and, in principle, provide an experimental characterization of the surface free energy sampling biases introduced by the charge distribution on the protein. The experimental results for ribonuclease A obtained using positive, neutral, and negatively charged small nitroxide radicals are qualitatively similar to those expected from electrostatic calculations. However, while systematic electrostatic trends are apparent, the three different combinations of the data sets do not yield internally consistent values for the electrostatic contribution to the intermolecular free energy. We attribute this failure to the weakness of the electrostatic sampling bias for charged nitroxides in water and local variations in effective translational diffusion constant at the water-protein interface, which enters the nuclear spin relaxation equations for the nitroxide-proton dipolar coupling.     

Pseudospin solitons in the coherent stripe phase of a bilayer quantum Hall system

In the Hartree–Fock approximation and at total filling factor ν=4N+1, the ground state of the two-dimensional electron gas in a double quantum well system in a quantizing magnetic field is, in some range of interlayer distances, a coherent striped phase. This stripe phase has one-dimensional coherent channels that support charged excitations in the form of pseudospin solitons. In this work, we compute the transport gap of the coherent striped phase due to the creation of soliton–antisoliton pairs using a supercell microscopic unrestricted Hartree–Fock approach. We study the energy gap as a function of interlayer distance and tunneling amplitude. Our calculations confirm that the soliton–antisoliton excitation energy is lower than the corresponding Hartree–Fock electron–hole pair energy.