Dipole Rotation Research Articles

Drug-amino acid interaction: Molecular dynamics in aqueous medium using time domain reflectometry

Present work reports dielectric response of the non-steroidal anti-inflammatory drug (NSAID) aceclofenac in aqueous valine solutions at various concentrations and temperatures (278.15 K–298.15 K) in the frequency range of 0.01 GHz to 30 GHz using Time-domain reflectometry (TDR) technique. The frequency dependent complex dielectric permittivity has been analyzed by Harviliak-Negami equation. Debye model is used for the description of complex dielectric permittivity spectra ε*(ν). The structural and dynamical properties of water has been investigated at different concentrations of valine and aceclofenac using dielectric as well as thermodynamic parameters that includes static dielectric constant (ε0), relaxation time (τ0), Kirkwood correlation factor (g), free energy of activation (ΔF), entropy of activation (ΔS), and enthalpy of activation (ΔH). Towards the measured low temperature and high concentrations of Valine and Aceclofenac (ACF), static dielectric constant (ε0) was found to be increasing. This could be due to increased effective dipole-dipole parallel alignment and can be confirmed by the increasing values of correlation factor (g > 1). The dipole-dipole interaction between Drug-Amino acid resulted in increased dielectric relaxation time (τ0) of system due to increased steric hindrance for the rotation of dipoles. The free energy of activation was found to be in the range of 2.22 and 2.58 Kcal mol-1. The entropy is more negative at high concentration suggesting more ordered structure. The slope of log (Tτ0) vs. 1000/T gives the value of enthalpy (ΔH).

In Quest of the Missing C2H6O2 Isomers in the Interstellar Medium: A Theoretical Search.

Ethylene glycol (C2H6O2), the only diol detected in the interstellar medium (ISM), is a key component in the synthesis of prebiotic sugars. Its structural isomer, methoxymethanol, has also been found in the ISM. Our results show that neither ethylene glycol (ethane-1,2-diol) nor methoxymethanol is the most stable isomer. Using high-level computational methods, we identified five isomers: two diols, one hydroxy ether, and two peroxides. The geminal diol 1,1-ethanediol (ethane-1,1-diol) is the most stable isomer, although it has not been detected in the ISM, whereas the two peroxides are less stable than the geminal diol by 60 kcal/mol. This study also provides the rotational constants and dipole moment for each conformer of every C2H6O2 isomer.

The Halogenation Effect Induces a Variety of Switchable Phase Transition and Second-Harmonic-Generation Materials.

Halogen engineering offers a means of enhancing the physical properties of materials by fine-tuning the rotational energy barrier and dipole moment, which proved to be effective in achieving switchable phase transitions and optical responses in materials. In this work, by substituting the methyl group in ligand N-ethyl-1,5-diazabicyclo[3.3.0]octane (CH3CH2-3.3.0-Dabco) with halogen atoms X (Cl or Br) and then contining to react it with FeBr3 in a HBr aqueous solution, we successfully synthesized three kinds of organic-inorganic hybrid switchable phase-change materials, [CH3CH2-3.3.0-Dabco]FeBr4 (1), [ClCH2-3.3.0-Dabco]FeBr4 (2), and [BrCH2-3.3.0-Dabco]FeBr4 (3), which were fully characterized by single-crystal X-ray diffraction and variable-temperature powder X-ray diffraction. Compared to compound 1, compounds 2 and 3 show two pairs of reversible phase transitions, dielectric anomalies, and a second-harmonic-generation effect, which are successfully induced due to the halogen substitution. This study offers an effective molecular design strategy for the exploration and construction of iron halide organic-inorganic hybrid materials with temperature-adjustable physical properties.

An approximate Kerr–Newman-like metric endowed with a magnetic dipole and mass quadrupole

Approximate all-terrain spacetimes for astrophysical applications are presented. The metrics possess five relativistic multipole moments, namely, mass, rotation, mass quadrupole, charge, and magnetic dipole moment. All these spacetimes approximately satisfy the Einstein–Maxwell field equations. The first metric is generated using the Hoenselaers–Perjés method from given relativistic multipoles. The second metric is a perturbation of the Kerr–Newman metric, which makes it a relevant approximation for astrophysical calculations. The last metric is an extension of the Hartle–Thorne metric that is important for obtaining internal models of compact objects perturbatively. The electromagnetic field is calculated using Cartan forms for locally non-rotating observers. These spacetimes are relevant for inferring properties of compact objects from astrophysical observations. Furthermore, the numerical implementations of these metrics are straightforward, making them versatile for simulating potential astrophysical applications.

Freezing of Water Solvation Dynamics in Nanoconfinement by Reverse Micelles at Room Temperature.

Much attention has recently been paid to anomalously low dielectric constants of nanoconfined water between two slabs at room temperature (Fumagalli et al. Science, 2018, 360, 1339). These low values imply that the dipole rotation of the interfacial water on the slab is completely suppressed. Such freezing has so far been observed for water confined between solids. In contrast, it remains unclear whether this holds for water in soft confinement, which is omnipresent naturally and artificially. Here, we address this question using encapsulated reverse micelles with a dye molecule, allowing us to study water sandwiched between the surfactant and dye molecules in solution. Moreover, we examine the solvation related to the dielectric property of water, which is reorientational motion in the hydration layer of the dye molecule, by persistent hole-burning spectroscopy. We first show that the dye molecule is surrounded by water without contact with the surfactant and that the dye molecule has two or three hydration layers on average. We next demonstrate that the solvation dynamics is frozen below the water droplet size of ∼4 nm, whereas they become liquid-like when the RM size is further increased. The average gap distance (∼1.5 nm) for freezing the solvation agrees with the gap distance with no rotational water motions between slabs. Our findings may have biological relevance, providing a new aspect for understanding biological function in cells.

Ground states of planar dipolar rotor chains with recurrent neural networks

In this contribution, we employ a recurrent neural network (RNN) architecture in a variational optimization to obtain the ground state of linear chains of planar, dipolar rotors. We test different local basis sets and discuss their impact on the sign structure of the many-body ground state wavefunction. It is demonstrated that the RNN ansatz we employ is able to treat systems with and without a sign problem in the ground state. For larger chains with up to 50 rotors, accurate properties, such as correlation functions and Binder parameters, are calculated. By employing quantum annealing, we show that precise entanglement properties can be obtained. All these properties allow one to identify a quantum phase transition between a paraelectric and a ferroelectric quantum phase.

Interface-induced dual-pinning mechanism enhances low-frequency electromagnetic wave loss

Improving the absorption of electromagnetic waves at low-frequency bands (2-8 GHz) is crucial for the increasing electromagnetic (EM) pollution brought about by the innovation of the fifth generation (5G) communication technology. However, the poor impedance matching and intrinsic attenuation of material in low-frequency bands hinders the development of low-frequency electromagnetic wave absorbing (EMWA) materials. Here we propose an interface-induced dual-pinning mechanism and establish a magnetoelectric bias interface by constructing bilayer core-shell structures of NiFe2O4 (NFO)@BiFeO3 (BFO)@polypyrrole (PPy). Such heterogeneous interface could induce distinct magnetic pinning of the magnetic moment in the ferromagnetic NFO and dielectric pinning of the dipole rotation in PPy. The establishment of the dual-pinning effect resulted in optimized impedance and enhanced attenuation at low-frequency bands, leading to better EMWA performance. The minimum reflection loss (RLmin) at thickness of 4.43 mm reaches -65.30 dB (the optimal absorption efficiency of 99.99997%), and the effective absorption bandwidth (EAB) can almost cover C-band (4.72 ~ 7.04 GHz) with low filling of 15.0 wt.%. This work proposes a mechanism to optimize low-frequency impedance matching with electromagnetic wave (EMW) loss and pave an avenue for the research of high-performance low-frequency absorbers.

Minimal Coarse-Grained Models of Polar Solvent for Electrolytes: Stockmayer Versus Dumbbell.

This study explores the potential of the dumbbell solvent as a minimal model for understanding electrolyte solutions in polar solvents. Our investigation involves a comparative analysis of the dumbbell model and the Stockmayer model, focusing on ion solvation and ion-ion correlations. We examine electrolytes containing symmetric monovalent salts dissolved in polar solvents while varying the ion density and solvent polarity. Both models predict an augmented solvent coordination number around ions as the solvent polarity increases, with the dumbbell solvent displaying a more pronounced effect. Notably, radial distribution functions (RDFs) between solvent and ions yield differing trends; Stockmayer models exhibit a nonmonotonic relationship due to strong dipole-dipole interactions at higher polarity, while RDFs for ions and dumbbell solvents consistently rise. In response to increased solvent polarity, Stockmayer solvents within the ion's solvation shell undergo continuous dipole orientation shifts, whereas the dumbbell solvent predominantly adopts pointing-away dipole orientations, diminishing pointing-to orientations. This underscores the significance of the interplay between the solvent molecular orientation and dipole rotation. Both models qualitatively predict ion pairing and clustering behaviors across varying solvent dipole strengths and salt concentrations. The Stockmayer solvent generally provides stronger electrostatic screening than the dumbbell solvent due to its neglect of the coupling between molecular orientation and dipole rotation. What's more, at a high dipole moment regime, ion-ion correlations in Stockmayer solvent can become stronger with increasing dipole moment due to stronger solvent-solvent correlations. This study underscores the effectiveness of the dumbbell solvent model in systematically elucidating the fundamental principles governing electrolytes and offers potential applications in the rational design of electrolyte systems.

Electromagnetism - Properties of Erythrocytes

At the onset of blood flow, red blood cells (RBCs) align along the central plane of the vessels. In capillaries, RBCs transform from a biconcave disk into a parachute shape. As blood transitions from the arterial to the venous end, the hemoglobin in erythrocytes alters its magnetic susceptibility. Within approximately 0.6-0.8 seconds, oxygen is displaced from RBCs through diffusion. This study explores the fundamentals and interconnections of these processes.
 
 Blood samples from 35 different healthy individuals were analyzed. The research examined magnetic field induction in ferromagnetic toroids, formed by the alternative electric field with a square wave signal, and studied the AC in the secondary coil - a tube filled with blood. This study discusses the impact of RBC geometry and hemoglobin allosteric transitions on electric signal generation and its relevance to cellular metabolic activity in the body.
 
 The findings suggest that the AC field, originating from the heart's rotational dipole, can generate a magnetic field in RBCs, facilitating the allosteric transformations of hemoglobin. Hemoglobin's thermoelastic expansion and magnetostriction cause biconcave membrane oscillations at ultrasound frequencies. The resulting electroacoustic wave rotates charges at the cell's z-potential area, aids RBC migration into the flow plane, and enhances trans capillary diffusion of substances.
 
 An electroacoustic standing wave emerges between the oscillating RBCs, coinciding with the wavenumber of externally penetrating infrared light. The synergic influence on hemoglobin in capillaries causes the RBC membrane to create a temporally frequency-modulated wave, carrying resonance molecular frequencies. This wave regulates biochemical processes within and outside body cells.

2D hexagonal assembly of a dipolar rotor with a close interval of 0.8 nm using a triptycene-based supramolecular scaffold.

Controlling the rotation of carbon-carbon bonds, which is ubiquitous in organic molecules, to create functionality has been a subject of interest for a long time. In this context, it would be interesting to explore whether cooperative and collective rotation could occur if dipolar molecular rotors were aligned close together while leaving adequate space for rotation. However, it is difficult to realize such structures as bulk molecular assemblies, since molecules generally tend to assemble into the closest packing structure to maximize intermolecular forces. To tackle this question, we examined an approach using a supramolecular scaffold composed of a tripodal triptycene, which has been demonstrated to strongly promote the assembly of various molecular and polymer units into regular "2D hexagonal packing + 1D layer" structures. We found that a molecule (1) consisting of a dipolar 1,2-difluorobenzene rotor sandwiched by two 10-ethynyl-1,8,13-tridodecyloxy triptycenes, successfully self-assembles into the desired structure, where the dipolar rotor units align two-dimensionally at a close interval of approximately 0.8 nm while having a degree of freedom for rotational motion. Here we describe the self-assembly behavior of 1 in comparison with the general trend in molecular self-assembly, as well as the motility of the two-dimensionally aligned molecular rotors investigated using solid-state 19F-MAS NMR spectroscopy.

Polarization effects on the rotational gyromagnetic ratio and magnetic dipole moments of 175,177,177mYb

Polarization effects on the rotational gyromagnetic ratio and magnetic dipole moments of 175,177,177mYb

Performance Evaluation of DFTB1 and DFTB2 Methods in reference to the Crystal Structures and Molecular Energetics of Siloxaalkane Molecular Compass

In the lately developed computational paradigms and state-of-art theoretical analyses, the density-functional based tight-binding (DFTB) scheme and its profound theoretical features extended to address the crystalline molecular systems stand as the most versatile quantum mechanical method. Being its computational parser codes extremely efficient and even assessable directly as a low-cost scheme despite hosting ab initio functionalities comprising mathematical formulations, the “non-self-consistent-charge” (DFTB1) and “self-consistent-charge" (DFTB2) approaches are extensively applied to the wide ranged molecular systems under both crystalline (PBC) and non-crystalline conditions. The "dispersion energy corrections (DECs)" features of it further add an additional value to their rational applications. Herewith, the intensive evaluations on their performances are carried out based on the results they produced for the experimentally synthesized amphidynamic type molecular crystal with macroscopic compass like supramolecular assembly possessing central dipolar difluorophenylene rotator (compass needle), axial Si-C bond spin axis, and peripheral -Si- & -Si-O- made siloxaalkane stator. It is found that the DFTB2 performed far better than the DFTB1 in reference to its datasets: (a) lengths for the bonds associated with rotator, stator, and spin axis, (b) free-volume unit around the rotator, (c) rotational energy barriers, viz. = 5.99 kcal/mol, & 5.52 kcal/mol under PBC with and without DECs, and (d) locations of the 1p-flipped (rotator) degenerate equilibrium structures, viz. at f = 0.505p & 1.493p (Expt. f = 0.56p & 1.56p) radians. Besides this, the dispersion constants for the F atom; cutoff =3.8Å, polarizability =3.4Å3, and effective nuclear charge =3.5au determined by DFTB2, and the precise unit-cell geometries derived by undertaking these numeral values further exemplified its superiority over DFTB1. It is believed that all the justifications and quantitative interpretations conferred throughout this article put considerable demands on the accuracy of DFTB2 for investigating crystal structures and molecular energetics explicitly.

Significantly enhanced performance and conductivity mechanism in Nb/Mn co-doped CaBi4Ti4O15 ferroelectrics

With the rapid development of high-end industries, the demand for high-temperature piezoelectric materials is significantly increasing. However, realizing the ultra-high performance to meet more applications still faces major scientific and engineering challenges of our time. Here, a new Nb/Mn co-doped CaBi4Ti4O15 (CBT) high-temperature piezoelectric material system of CaBi4Ti4-x(Nb2/3Mn1/3)xO15 was synthesized by the conventional solid-state sintering method. The results show that the addition of the dopants tends to break the long-range ferroelectric chain and soften the flexibility of polarization, resulting in more distorted crystal structure and better ferroelectric properties of CBT ceramics. The ultra-high piezoelectric constant (d33 = 26.8 pC/N) is thus attained in CBT-based ceramics with x = 0.12, which is about several times larger than that of pure CBT ceramics. Moreover, numerous nano-sized layered domain structures that lie on the lateral plane of grains are observed in ceramics, with lower domain wall energy and better dynamic features under electric fields, mainly responsible for the origin of enhanced performance. Besides, excess dopants could make the conductivity mechanism of CBT ceramics transform from p-type to n-type, and also result in a shift of conduction relaxation mechanism from defect dipole rotation polarization to electron relaxation polarization. The work not only provides a promising candidate for high-temperature piezoelectric materials, but also opens a window for optimizing performance by tailoring domain structures using chemical modification.

Molecular Mechanism of the Piezoelectric Response in the β-Phase PVDF Crystals Interpreted by Periodic Boundary Conditions DFT Calculations.

A theoretical approach based on Periodic Boundary Conditions (PBC) and a Linear Combination of Atomic Orbitals (LCAO) in the framework of the density functional theory (DFT) is used to investigate the molecular mechanism that rules the piezoelectric behavior of poly(vinylidene fluoride) (PVDF) polymer in the crystalline β-phase. We present several computational tests highlighting the peculiar electrostatic potential energy landscape the polymer chains feel when they change their orientation by a rigid rotation in the lattice cell. We demonstrate that a rotation of the permanent dipole through chain rotation has a rather low energy cost and leads to a lattice relaxation. This justifies the macroscopic strain observed when the material is subjected to an electric field. Moreover, we investigate the effect on the molecular geometry of the expansion of the lattice parameters in the (a, b) plane, proving that the rotation of the dipole can take place spontaneously under mechanical deformation. By band deconvolution of the IR and Raman spectra of a PVDF film with a high content of β-phase, we provide the experimental phonon wavenumbers and relative band intensities, which we compare against the predictions from DFT calculations. This analysis shows the reliability of the LCAO approach, as implemented in the CRYSTAL software, for calculating the vibrational spectra. Finally, we investigate how the IR/Raman spectra evolve as a function of inter-chain distance, moving towards the isolated chain limit and to the limit of a single crystal slab. The results show the relevance of the inter-molecular interactions on the vibrational dynamics and on the electro-optical features ruling the intensity pattern of the vibrational spectra.

Dielectric Study of Liquid Crystal Dimers: Probing the Orientational Order and Molecular Interactions in Nematic and Twist-Bend Nematic Phases.

Dielectric spectroscopy in frequencies that range from 10 Hz to 1 GHz has been used to study the molecular orientational dynamics of the two types of dimers that form the twist-bend nematic phase over a wide range of temperatures for both nematic and twist-bend nematic phases. The symmetrical and asymmetrical liquid crystal dimers with the cyanobiphenyl mesogenic groups were investigated. The results were analyzed within the framework of the molecular theory of dielectric permittivity for nematogens. The two molecular processes can be assigned to the reorientation of the monomeric unit: the high frequency one to the precessional rotation of the longitudinal components of the cyanobiphenyl groups (CN) and the second (low frequency) to the end-over-end rotation of the CN dipole around the short molecular axis. The precession mode, which is determined by the local order and is almost unaffected by the phase transition from the nematic to the twist-bend phase, while the end-over-end rotation clearly slowed down at the transition, as it is affected by the growth of the intermolecular interactions. The latter corresponds well to the fact revealed by IR spectroscopy about the longitudinal correlation of the molecular dipoles.

Pyroelectric energy conversion efficiency of ferroelectrics in Olson cycle

Phenomenology theory of ferroelectrics is developed to solve pyroelectric energy conversion performances in Olson cycle by using rotation and coupling of dipoles depending on temperature and electric field. Numerical simulation shows electric field related pathway of cycle. The conversion efficiency of an Olson cycle has a peak at temperature over Curie temperature, which is higher for increased low temperature point. A horary conversion efficiency is developed to compare conversion efficiencies in different temperature range. The conclusion is that the horary efficiency is higher when the low temperature point is higher and the high temperature is lower.

X-ray polarimetry of X-ray pulsar X Persei: another orthogonal rotator?

ABSTRACT X Persei is a persistent low-luminosity X-ray pulsar of period of ≈ 835 s in a Be binary system. The field strength at the neutron star surface is not known precisely, but indirect signs indicate a magnetic field above 1013 G, which makes the object one of the most magnetized known X-ray pulsars. Here we present the results of observations X Persei performed with the Imaging X-ray Polarimetry Explorer (IXPE). The X-ray polarization signal was found to be strongly dependent on the spin phase of the pulsar. The energy-averaged polarization degree in 3–8 keV band varied from several to ∼20 per cent over the pulse with a phase dependence resembling the pulse profile. The polarization angle shows significant variation and makes two complete revolutions during the pulse period, resulting in nearly nil pulse-phase averaged polarization. Applying the rotating vector model to the IXPE data we obtain the estimates for the rotation axis inclination and its position angle on the sky, as well as for the magnetic obliquity. The derived inclination is close to the orbital inclination, reported earlier for X Persei. The polarimetric data imply a large angle between the rotation and magnetic dipole axes, which is similar to the result reported recently for the X-ray pulsar GRO J1008−57. After eliminating the effect of polarization angle rotation over the pulsar phase using the best-fitting rotating vector model, the strong dependence of the polarization degree with energy was discovered, with its value increasing from 0 at ∼2 keV to 30per cent at 8 keV.

Dipolar Energy as an Electrical Power Source: Dipole Rotation in Solids Enables a New Source for the Triboelectric Generator

Herein, the concept of triboelectric generators using dipolar polarization energy as an electrical power source is introduced. Dipolar polarization energy is stored in dielectric films by rubbing, and is conveyed to external circuits for use during the depolarization process. Pyromellitic dianhydride‐4,4’‐oxydianiline polyimide films are used as a possible candidate for triboelectric generators, where polarization is formed by rubbing owing to the orientational alignment of polar molecular groups. The current–voltage measurements are used to evaluate the equivalent‐circuit parameters of the generator. The current source is 0.07 nA at 30 °C, which is enhanced to 0.13 nA at 110 °C. It is indicated in these results that the depolarization process proceeds in a short time at higher temperatures, causing an increase in the current. Consequently, the maximum power increases from 18 nW (30 °C) to 33 nW (110 °C). The enhancement of the output power at higher temperatures well supports the idea of using dipolar polarization energy as a power source of triboelectric generators.

Anisotropic motion of an electric dipole in a photon gas near a flat conducting boundary

The quantum Brownian motion of a single neutral particle with nonzero electric dipole moment placed in a photon gas at fixed temperature and close to a conducting wall is here examined. The interaction of the particle with the photon field leads to quantum dispersions of its linear and angular momenta, whose magnitudes depend on the temperature, distance to the wall, and also on the dipole moment characteristics. It is shown that for typical experimental parameters the amount of energy held by the dipole rotation is expressively larger than the one related to the center of mass translation. Furthermore, the particle kinetic energy in presence of a thermal bath can decrease if the wall is added to the system, representing a novel quantum cooling effect where the work done by the quantum vacuum extracts energy from the particle. Finally, possible observable consequences are discussed.

Domain wall saddle point morphology in ferroelectric triglycine sulfate

Ferroelectric domain walls, across which there is a divergence in polarization, usually have enhanced electrical conductivity relative to bulk. However, in lead germanate, head-to-head and tail-to-tail walls are electrically insulating. Recent studies have shown that this is because, when oppositely oriented domains meet, polar divergence is obviated by a combination of domain bifurcation and suspected local dipolar rotation. To explore the uniqueness, or otherwise, of this microstructure, we have used tomographic piezoresponse force microscopy to map three-dimensional domain morphologies in another uniaxial ferroelectric system: triglycine sulfate. This mapping reveals an abundance of domain wall saddle points, which are characteristic of interlocking bifurcated domains. Conducting atomic force microscopy, performed close to the saddle points, showed no evidence for highly localized conducting domain wall sections, across which a divergence in polarization might be implied; this supports the notion that localized dipolar rotation occurs to minimize any potential polar discontinuity. Overall, our study, therefore, confirms that mutual domain bifurcation and suspected local dipolar rotation are not unique to lead germanate and instead may be widely present in other uniaxial ferroelectrics.