Dipolar Contributions Research Articles

Modeling Micellar Growth and Branching in Mixtures of Zwitterionic with Ionic Surfactants.

Zwitterionic surfactants are widely applied as drag-reducing or thickening agents because their aggregation patterns may drastically change in response to variations of the system composition or external stimuli, which provides controllable viscoelasticity. For predicting aggregation behavior of surfactant mixtures, classical molecular thermodynamic models have been widely used. Particularly, the results of modeling have been reported for zwitterionic/ionic surfactant mixtures. However, for solutions containing a zwitterionic surfactant, no molecular thermodynamic model has been proposed for a micellar branch. In this work we extend the classical molecular thermodynamic aggregation model to describe aggregation in the aqueous mixtures that contain a zwitterionic and an ionic surfactant. We derive analytical expressions (1) for the contribution of dipoles to the electrostatic term of the standard free energy of aggregation into micellar branches and (2) for the dipolar contribution to the persistence length of wormlike micelles. The dependence of micellar branching on the surfactant concentration is taken into account by including the population of micellar branches in the material balance equations. This model is applied to predict aggregation equilibrium in aqueous salt solutions of betaine (oleoylamidopropyl-N,N-dimethylbetaine) mixed with sodium dodecyl sulfate (SDS) and the longer tail sodium n-alkyl sulfates. We discuss the predicted properties of the aggregates and micellar networks and compare our predictions with available experimental data.

The quasi bound spectrum of H2

We compute the radiative ro-vibrational emission spectrum of H involving quasi-bound states via a simple numerical method of resolution of the Schrödinger equation by introducing a modified effective molecular potential. The comparison of the eigenvalues obtained with our approximation and other theoretical methods based on scattering resonance properties is excellent. Electric quadrupole and magnetic dipole contributions are calculated and we confirm the previous computations of Forrey of the electric quadrupole transition Einstein coefficients. The astrophysical relevance of such quasi-bound levels is emphasized.

Possibility of Measurement of the Three-Spin Dipolar Contribution to Nuclear Spin–Lattice Relaxation in Solids by the Conventional Pulse NMR Technique

Possibility of Measurement of the Three-Spin Dipolar Contribution to Nuclear Spin–Lattice Relaxation in Solids by the Conventional Pulse NMR Technique

Water Structure in the Electrical Double Layer and the Contributions to the Total Interfacial Potential at Different Surface Charge Densities.

The electric double layer governs the processes of all charged surfaces in aqueous solutions; however, elucidating the structure of the water molecules is challenging for even the most advanced spectroscopic techniques. Here, we present the individual Stern layer and diffuse layer OH stretching spectra at the silica/water interface in the presence of NaCl over a wide pH range using a combination of vibrational sum frequency generation spectroscopy, heterodyned second harmonic generation, and streaming potential measurements. We find that the Stern layer water molecules and diffuse layer water molecules respond differently to pH changes: unlike the diffuse layer, whose water molecules remain net-oriented in one direction, water molecules in the Stern layer flip their net orientation as the solution pH is reduced from basic to acidic. We obtain an experimental estimate of the non-Gouy-Chapman (Stern) potential contribution to the total potential drop across the insulator/electrolyte interface and discuss it in the context of dipolar, quadrupolar, and higher order potential contributions that vary with the observed changes in the net orientation of water in the Stern layer. Our findings show that a purely Gouy-Chapman (Stern) view is insufficient to accurately describe the electrical double layer of aqueous interfaces.

Electric field enhancement by a hybrid dielectric-metal nanoantenna with a toroidal dipole contribution.

Plasmonic nanocavities enable extreme light-matter interactions by pushing light down to the nanoscale. The numerical simulation is carried out systematically on the slotted Φ-shaped Si disk system with the super-dipole mode based on the analysis of the scattering strength of electric and toroidal dipoles. New blocks are introduced to the zero-field strength region of a slotted Si disk system as a function of the field enhancement factors. The far-field scattering characteristics and near-field electromagnetic field distributions are investigated by a multipole decomposition analysis to elucidate the intrinsic causes of the field enhancement. In the hybrid metal-dielectric nanoantenna, the Φ-shaped Si structure is prepared by superimposing Au nanoantennas for further field enhancement. In addition, the effects of the placement of an electric dipole emitter on the Purcell factor are derived. The geometric volume of the system is increased, and the electric field strength is improved, leading to an electric field increase of ∼30. Coupling between the super-dipole mode of the dielectric nanostructure and plasmonic modes of the metallic nanoantenna produces an enhancement as large as 16 times. Our results reveal a greatly enhanced super-dipole mode by electromagnetic coupling in composite structures, which will play a significant role in enhanced nonlinear photonics, near-field enhancement spectroscopy, and strong photon-exciton coupling.

Possible formation mechanism of multistate gravitational atoms

The collision of two equilibrium ground state solutions of the Schr\"odinger-Poisson (SP) system, in orthogonal states, is proposed as a formation mechanism of mixed state solutions of the SP system with spherical and first dipolar components. The collisions are simulated by solving numerically the SP system for two orthogonal states, considering head-on encounters, and using various mass ratios between the initial configurations with different head-on momentum. The results indicate that the less massive of the configurations pinches-off the more massive one, and redistributes its density along the axis of collision. The averaged in time density of the two states resembles the distribution of matter of bi-state equilibrium configurations with monopolar and dipolar contributions.

Dipolar and Contact Paramagnetic NMR Chemical Shifts in AnIV Complexes with Dipicolinic Acid Derivatives.

Actinide +IV complexes (AnIV = ThIV, UIV, NpIV, and PuIV) with two dipicolinic acid derivatives (DPA and Et-DPA) have been studied by 1H and 13C NMR spectroscopies and first-principles calculations. The Fermi contact and dipolar contributions to the actinide-induced shifts (AIS) are evaluated from a temperature dependence analysis, combined with ab initio results. It allows an experimental estimation of the axial anisotropy of the magnetic susceptibility Δχax and of the hyperfine coupling constants of the NMR-active nuclei. Due to the compactness of the coordination sphere, the magnetic anisotropy of the paramagnetic center is small, and this makes the contact contribution to be the dominant one, even on the remote atoms. The sign of the hyperfine coupling constants and related spin densities is alternating on the nuclei of the ligand cycle, denoting a preponderant spin polarization mechanism. This is well reproduced by unrestricted density functional theory (DFT) calculations. Those values are furthermore slightly decreasing in the actinide series, which indicates a small decrease of the covalency from UIV to PuIV.

A new power spectrum and stochastic representation for the geomagnetic axial dipole

SUMMARY Earth’s internal magnetic field is dominated by the contribution of the axial dipole whose temporal variations are wide ranging and reflect characteristic timescales associated with geomagnetic reversals and large scale palaeosecular variation, ranging down to decadal and subannual field changes inferred from direct observations. We present a new empirical power spectrum for the axial dipole moment based on composite magnetic records of temporal variations in the axial dipole field that span the frequency range 0.1 to 5 × 105 Myr–1 (periods from 10 million to 2 yr). The new spectrum is used to build a stochastic representation for these time variations, based on an order 3 autoregressive (AR) process and placed in the context of earlier stochastic modelling studies. The AR parameter estimates depend on the frequency of transitions in the spectral regime and may be influenced by Ohmic diffusion, advection and torsional oscillations in Earth’s core. In several frequency ranges across the interval 200–5000 Myr–1(5000 to 200 yr periods) the empirical power spectrum lies above the AR3 model and may be influenced by Magneto–Coriolis (MC) waves in Earth’s core. The spectral shape and parameter estimates provide a potentially useful guide for developing assessments of whether numerical dynamo simulations meet criteria for being considered Earth like.

Spectroscopic investigation of dysprosium doped bismuth-borate glasses for white light application

In this work, the spectroscopic properties of Dysprosium doped lithium-bismuth-borate glasses were investigated for different photonic and lasing applications. The photon absorption was observed in Uv–Vis–NIR region. Using Jud-Ofelt analysis the electric and magnetic dipole contribution were calculated to determine the parameters (Ω = 2, 4, 6), radiative lifetime and branching ratios of BBiLDy15 glass. The visible luminescence spectra at 482, 576, 663 and 772-nm correspond to transitions 4F9/2 → 6HJ (J = 15/2, 13/2, 11/2, 9/2) under λex = 350 nm were observed. The lasing parameters like stimulated emission cross section (5.45 × 10−22 cm2) and experimental branching ratio (61%) of the BBiLDy1.5 glass were determined from the visible transitions in the PL-emission spectra. The decrease in life time value of glass samples was observed that was attribute to the energy transfer via resonance energy transfer (RET) from host matrix to luminescence centers. The CIE chromaticity color co-ordinates, CCT results and the emission cross section for the visible transitions emphasizing the capacity of BBiLDy glass samples as potential material for white light emitting diodes and visible laser application.

Heat capacity of molten alkali halides

Experimental data on the heat capacities of molten alkali halides near their melting points are analyzed depending on cation–anion composition. The isochoric heat capacities of all 20 liquid alkali halides were calculated using thermodynamic perturbation theory (TPT) based on a reference system of charged hard spheres + charge-induced dipole contribution to pairwise ionic interaction. Changes in the heat capacity depending on the ratio of ionic radii and polarizabilities are identified and described. On this basis, recommended heat capacity values are selected from the various experimental data. It is shown that the reduced isochoric heat capacity (CV/kB) should increase with a mismatch in the cation and anion radii as an even function with a minimum. Charge-induced dipole interactions lead to a breaking of the specific Coulomb symmetry, resulting in a more significant increase in the heat capacity for salts containing the smallest cations, as well as the anions with largest size and polarizability.

Ultrafast transverse and longitudinal response of laser-excited quantum wires.

We couple 1D pulse propagation simulations with laser-solid dynamics in a GaAs quantum wire, solving for the electron and hole populations and the interband and intraband coherences between states. We thus model not only the dynamical dipole contributions to the optical polarization (interband bound-charge response) but also the photo-generation and back-action effects of the net free-charge density (intraband free-charge response). These results show that solving for the dynamic electron and hole intraband coherences leads to plasma oscillations at THz frequencies, even in a 1D solid where plasma screening is small. We then calculate the transverse and longitudinal response of the quantum wire and characterize the dispersion relation for the e-h plasma. This approach allows one to predict the optoelectronic response of 1D semiconductor devices during and after exposure to resonant ultrashort pulses.

Study of short range and long range molecular interactions in binary liquid mixtures of N,N-dimethylformamide (DMF) and 1-propanol

In the present study precisely measured properties; static dielectric constant (ε0), refractive index (n) and density (ρ) of binary liquid mixtures of N,N-dimethylformamide (DMF) and 1-propanol (1-PN) have been used to determine linear correlation parameter (grr), mutual linear correlation parameter (gAB), excess Helmholtz free energy functions (ΔF) and excess molar polarization (ΔP). The dipolar contributions to these functions arising from long range electrostatic interaction, short range interaction between identical molecules and short range interaction between dissimilar molecules have been assessed separately. The excess thermodynamic functions calculated from the experimental data supports the formation of clusters with antiparallel or destructive angular correlation (β-clusters). The variation of excess static dielectric constant, excess refractive index and excess molar volume have been used to discuss the type, the strength and the nature of intermolecular interactions betweenconstituent species. Comparison of the predicted values of static dielectric constant and refractive index of the liquid mixtures using various mixing rules with the experimentally determined values have been assessed in terms of Average Percentage Deviation (APD).

Time-periodic interaction between a spin-pair: A quantum master equation approach

Quantum master equations describe the dynamics of open quantum systems. Such systems might be subjected to external drives and internal interactions such as direct dipolar couplings. Both the external drives and the internal interactions could be oscillatory functions of time. In particular, a spin pair undergoing magic angle sample spinning experiences such oscillatory interactions in time. In the present work, we analyze a spin pair with a time-periodic interaction by using our recently-proposed fluctuation-regulated quantum master equation [PRA, 97, 063837 (2018)] (FRQME). FRQME helps calculate the first as well as the second-order effects of all time-dependent interactions Hamiltonians. Using FRQME, we find the usual sideband pattern and also have shown the linewidths of the sidebands as a function of the coupling strength, the period of oscillation, and an environmental parameter. We show that at high spinning speed, the sidebands would have a Lorentzian shape. We predict that the dipolar contributions to the sidebands’ linewidths are smaller for a shorter correlation time of the environmental fluctuations.

The emergence of macroscopic currents in photoconductive sampling of optical fields

Photoconductive field sampling enables petahertz-domain optoelectronic applications that advance our understanding of light-matter interaction. Despite the growing importance of ultrafast photoconductive measurements, a rigorous model for connecting the microscopic electron dynamics to the macroscopic external signal is lacking. This has caused conflicting interpretations about the origin of macroscopic currents. Here, we present systematic experimental studies on the signal formation in gas-phase photoconductive sampling. Our theoretical model, based on the Ramo–Shockley-theorem, overcomes the previously introduced artificial separation into dipole and current contributions. Extensive numerical particle-in-cell-type simulations permit a quantitative comparison with experimental results and help to identify the roles of electron-neutral scattering and mean-field charge interactions. The results show that the heuristic models utilized so far are valid only in a limited range and are affected by macroscopic effects. Our approach can aid in the design of more sensitive and more efficient photoconductive devices.

Non-dipole effects on angular distribution of photoelectrons in sequential two-photon double ionization of Ar atom and K<sup>+</sup> ion

Owing to the development of XUV and X ray of the free-electron lasers, the photoelectron angular distribution in the sequential two-photon double ionization has received increasing attention of theorists and experimentalists, because it provides the valuable information about the electronic structure of atom or molecule systems and allows the obtaining of additional information about mechanisms and pathways of the two-photon double ionization. In this paper, the expression of the sequential two-photon double ionization process of the photoelectron angular distributions, including the non-dipole effects, is obtained based on the multi-configuration Dirac-Fock method and the density matrix theory, and the corresponding calculation code is also developed. Based on the code, the sequential two-photon double ionization process of the 3p and 2p shells of Ar atom and K<sup>+</sup> ion are studied, in which, the dipole and the non-dipole parameters of photoelectron angular distribution are investigated systematically. It is found that the angular distributions of the first- and second-step electrons in sequential two-photon double ionization are similar and the two photoionization processes affect each other. Near the ionization threshold, the photoionization cross-sections and anisotropy parameters for the 3p shell and the 2p shell show a large difference. While away from the threshold, the cross-section and angular anisotropy parameters of the 3p and 2p shells show similar behaviors. At the position of Cooper minimum of the photoionization cross section, the contribution of the electric dipole is suppressed, and the non-dipole effect is obvious. The non-dipole effect leads to a forward-backward asymmetric distribution of photoelectrons relative to the direction of incident light. The results of this paper will be helpful in studying the nonlinear processes of photon and matter interaction in the XUV range.

Dipolar pathways in dipolar EPR spectroscopy.

Dipolar electron paramagnetic resonance (EPR) experiments such as double electron-electron resonance (DEER) measure distributions of nanometer-scale distances between unpaired electrons, which provide valuable information for structural characterization of proteins and other macromolecular systems. To determine these distributions from the experimental signal, it is critical to employ an accurate model of the signal. For dilute samples of doubly spin-labeled molecules, the signal is a product of an intramolecular and an intermolecular contribution. We present a general model based on dipolar pathways valid for dipolar EPR experiments with spin-1/2 labels. Our results show that the intramolecular contribution consists of a sum and the intermolecular contribution consists of a product over individual dipolar pathway contributions. We examine several commonly used dipolar EPR experiments in terms of dipolar pathways and show experimental results confirming the theoretical predictions. This multi-pathway model makes it possible to analyze a wide range of dipolar EPR experiments within a single theoretical framework.

Weak correlation and strong relativistic effects on the hyperfine interaction in fluorine

In previous work devoted to ab initio calculations of hyperfine-structure constants in nitrogen and fluorine atoms, we observed sizable relativistic effects, a priori unexpected for such light systems, that can even largely dominate over electron correlation. We observed that the atomic wave functions calculated in the Breit-Pauli approximation describe adequately the relevant atomic levels and hyperfine structures, even in cases for which a small relativistic $LS$-term mixing becomes crucial. In the present work we identify levels belonging to the spectroscopic terms $2{p}^{4}{(}^{3}P)3d{\phantom{\rule{4pt}{0ex}}}^{2,4}(P,D,F)$ of the fluorine atom, for which correlation effects on the hyperfine structures are small, but relativistic $LS$-term admixtures are decisive to correctly reproduce the experimental values. The Breit-Pauli analysis of the hyperfine matrix elements nails cases with large cancellation, either between $LS$ pairs for individual hyperfine operators or between the orbital and the spin dipole contributions. Multiconfiguration Dirac-Hartree-Fock calculations are performed to support the Breit-Pauli analysis.

Balance of emission from THz sources in DC-biased and unbiased filaments in air

At the frequencies from 0.1 to 1 THz, we measured the angular distributions of terahertz (THz) emission from DC-biased femtosecond filament. The external electric field (DC bias) was increased from 0 to 3.3 kV/cm and provided continuous transition from forward conical emission, corresponding to the unbiased single-color filament, to on-axis emission, corresponding to the DC-biased one. We decomposed the measured far-field THz distributions into the quadrupole and dipole contributions, the latter being increased with increasing biasing field. The superposition of quadrupole and dipole local sources was integrated numerically over the plasma channel length and fit to the experimentally obtained angular distributions. The transition from the conical to the on-axis emission occured at the external field of (3.2 ± 0.8) kV/cm in the range of frequencies studied.

Superalkali-based alkalides Li3O@[12-crown-4]M (where M= Li, Na, and K) with remarkable static and dynamic NLO properties; A DFT study

Exploring new nonlinear optical materials with excess electron character is extremely important for promoting the application of excess electron compounds in nonlinear optics. Herein, by using density functional theory (DFT) computations, new superalkali-based alkalides Li3O@[12-crown-4]M− are designed as excess electron compounds. QTAIM studies suggest that the complexant interacts with alkali and superalkali clusters through non-covalent interactions. These complexes are thermodynamically stable and their interaction energies range from −33.40 ∼ −44.23 kcal mol-1. The alkalide nature of these compounds is guaranteed by their HOMOs values and NBO charge analysis. Being excess electron compounds, these alkalides shows potential electronic properties. Their HOMO-LUMO gaps ranging from 0.17–0.27 eV. With excellent properties, these complexes show remarkable total hyperpolarizability (βo) response (9.30×104–5.26×106au). Interestingly, the hyperpolarizability response is dependent on the size of alkali metals. The βvec values are quite comparable to total hyperpolarizability at the same level of theory. Furthermore, the hyperpolarizability calculated through two-level model (βtl) values show a trend similar to hyperpolarizability. Additionally, the dynamic hyperpolarizability response for EOPE effects is much pronounced at the dispersion frequency of 532 nm. The second hyperpolarizability response for the dc-Kerr constant is increased up to 2.75 × 1012 au which is much higher than those of previously reported alkalides. Strikingly, the frequency-dependent NLO response shows dependence on alkalide character rather than the size of alkali metal (M). Moreover, the βHRS value is recorded up to 2.16 × 106 au. The significant dipolar contribution to hyperpolarizabilities Φβ(J = 1) are observed for these complexes.

Structured light excitation of toroidal dipoles in dielectric nanodisks

Conventional electromagnetic multipoles can be completed by complementary sources of toroidal moments, opening the door to the engineering of nanophotonic devices. The main contribution of this study is comparing different light sources for enhancing the toroidal dipole response in a given system. We theoretically study the toroidal dipole excitation in an individual dielectric nanodisk by structured light illumination, including the tightly focused radially polarized beam and the focused doughnut pulse. The toroidal dipole and anapole can be excited by the interplay of the radial and longitudinal components of the incident light. As opposed to the plane wave illumination, the tightly focused radially polarized light can excite a near-ideal toroidal dipole while the contributions of the Cartesian electric dipole and other modes are significantly suppressed. We also show that the focused doughnut pulse is a promising tool for exciting a resonant toroidal response in nanophotonic systems. Furthermore, it is demonstrated that toroidal-driven field confinement leads to an enhancement of energy concentration inside the nanodisk that can potentially increase light harvesting and boost both linear and nonlinear light-matter interactions.