Dipole Vector Research Articles

T88. Optimizing lower limb Somatosensory Evoked Potentials (SEPs) with additional derivations

SEPs recorded over the scalp serve as surrogate markers of dorsal column proprioceptive pathway integrity during surgery. Changes in SEP amplitude and/or latency meeting “alarm criteria” can indicate neural injury and prompt the surgical team to take action. Alarm criteria (e.g. 50% drop in amplitude) lose specificity when SEP measurement variability is high (e.g. ⩾25%). Lower limb scalp SEPs has vary dipole vectors between individuals. Standard recording electrode derivations of SEPs have been shown to be suboptimal when compared to a derivation individually optimized for each patient. Scalp lower limb SEPs were monitored from a consecutive sample of 51 patients during non-emergent procedures at Mayo Clinic Rochester. Two additional scalp electrodes at Cz and Pz were setup beside the standard scalp electrodes (CPz, Fz, CPi and CPc). Two standard derivations (CPz-Fz and CPi-CPc) and five expanded derivations (CPz-CPc, Cz-CPc, Pz-CPc, CPz-CPi and Pz-Fz) were recorded. P38 amplitudes were measured for all derivations; the derivation with the lowest coefficient of variation (CV) and highest amplitude from each group (standard vs. expanded montage) were determined. The P38 with highest amplitude and lowest CV were found in the expanded montage in 78 (76%) and 71 (70%) out of 102 limbs from 51 patients. The expanded montage significantly lowered the minimum CV by 1.75% (P < 0.0001, linear regression) and increased the maximal amplitude by 0.13 μV (P < 0.0001, linear regression) as compared to the standard montage. The CPz-CPc was the most frequent derivation with lowest CV and highest amplitude among all seven derivations. The effort to implement an expanded scalp montage should be balanced with the potential improvements, which by our data, are only incremental. An expanded scalp montage may be highest yield in patients where recordings from a conventional montage are of poor quality.

Ampicillin permeation across OmpF, the major outer-membrane channel in Escherichia coli

The outer cell wall of the Gram-negative bacteria is a crucial barrier for antibiotics to reach their target. Here, we show that the chemical stability of the widely used antibiotic ampicillin is a major factor in the permeation across OmpF to reach the target in the periplasm. Using planar lipid bilayers we investigated the interactions and permeation of OmpF with ampicillin, its basic pH-induced primary degradation product (penicilloic acid), and the chemically more stable benzylpenicillin. We found that the solute-induced ion current fluctuation is 10 times higher with penicilloic acid than with ampicillin. Furthermore, we also found that ampicillin can easily permeate through OmpF, at an ampicillin gradient of 10 μm and a conductance of Gamp ≅ 3.8 fS, with a flux rate of roughly 237 molecules/s of ampicillin at Vm = 10 mV. The structurally related benzylpenicillin yields a lower conductance of Gamp ≅ 2 fS, corresponding to a flux rate of ≈120 molecules/s. In contrast, the similar sized penicilloic acid was nearly unable to permeate through OmpF. MD calculations show that, besides their charge difference, the main differences between ampicillin and penicilloic acid are the shape of the molecules, and the strength and direction of the dipole vector. Our results show that OmpF can impose selective permeation on similar sized molecules based on their structure and their dipolar properties.

On-the-Fly Ab Initio Semiclassical Evaluation of Absorption Spectra of Polyatomic Molecules beyond the Condon Approximation.

To evaluate vibronic spectra beyond the Condon approximation, we extend the on-the-fly ab initio thawed Gaussian approximation by considering the Herzberg-Teller contribution due to the dependence of the electronic transition dipole moment on nuclear coordinates. The extended thawed Gaussian approximation is tested on electronic absorption spectra of the phenyl radical and benzene; calculated spectra reproduce experimental data and are much more accurate than standard global harmonic approaches, confirming the significance of anharmonicity. Moreover, the extended method provides a tool to quantify the Herzberg-Teller contribution; we show that in the phenyl radical, anharmonicity outweighs the Herzberg-Teller contribution, whereas in benzene, the Herzberg-Teller contribution is essential because the transition is electronically forbidden and the Condon approximation yields a zero spectrum. Surprisingly, both adiabatic harmonic spectra outperform those of the vertical harmonic model, which describes the Franck-Condon region better. Finally, we provide a simple recipe for orientationally averaging spectra, valid beyond the Condon approximation, and a relation among the transition dipole, its gradient, and nonadiabatic coupling vectors.

Energy Band Gap Dependence of Valley Polarization of the Hexagonal Lattice

The origin of valley polarization of the hexagonal lattice is analytically discussed by tight binding method as a function of energy band gap. When the energy gap decreases to zero, the intensity of optical absorption becomes sharp as a function of k near the K (or K′) point in the hexagonal Brillouin zone, while the peak intensity at the K (or K′) point keeps constant with decreasing the energy gap. When the dipole vector as a function of k can have both real and imaginary parts that are perpendicular to each other in the k space, the valley polarization occurs. When the dipole vector has only real values by selecting a proper phase of wave functions, the valley polarization does not occur. The degree of the valley polarization may show a discrete change that can be relaxed to a continuous change of the degree of valley polarization when we consider the life time of photo-excited carrier.

Detection of Anomalous Dynamics for a Single Water Molecule.

Water dynamics is of predominant importance in life, and it plays a critical role in chemical and biological systems. Many studies have reported nonbulk and anomalous dynamics of water molecules; however, a general method to detect the anomalous dynamics is yet to be established. Here, we develop a detection approach for the anomalous dynamics of a water molecule. Using a time series of the dipole vector of a water molecule, our approach achieves single-molecule detection of the anomalous dynamics for all water molecules in the system. Moreover, our approach quantifies the anomalous dynamics of a water molecule, which enables users to compare between different systems. In addition to the applicability, our approach has computational efficiency because it never calculates interactions with any other molecules. Experiments on five different systems of molecular dynamics simulations illustrate that our approach successfully detects the change points of water-molecule dynamics. These results demonstrate that our approach is a useful tool and provides a better understanding of dynamics of water molecules.

Layered metal(IV) phosphonate materials: Solid-state 1 H, 13 C, 31 P NMR spectra and NMR relaxation.

Multinuclear solid-state NMR and powder X-ray diffraction data collected for phosphonate materials Zr(O3 PC6 H4 PO3 ) · 3.6H2 O and Sn(O3 PC6 H4 PO3 )0.85 (O3 POH)0.30 ·3.09H2 O have resulted in the layered structure, where the phosphonic acids cross-link the layers. The main structural motif (the 111 connectivity in the PO3 group) has been established by determination of chemical shift anisotropy parameters for phosphorus nuclei in the phosphonate groups. An analysis of the variable-temperature 31 PT1 measurements and the shapes of the phosphorus resonances in the 31 P static NMR spectra have resulted in the dipolar mechanism of the phosphorus spin-lattice relaxation, where the rotating phenylene rings reorient dipolar vectors P… H as a driving force of the relaxation process. It has been found that water protons do not affect the 31 PT1 times. The activation energy of the phenylene rotation in both compounds has been determined as low as 12.5kJ/mol. The interpretation of the phosphorus relaxation data has been independently confirmed by the measurements of 1 H T1 times for protons of the phenylene rings.

Supramolecular Polymerization of N,N',N″,N‴-tetra-(Tetradecyl)-1,3,6,8-pyrenetetracarboxamide: A Computational Study.

The role of molecular dipole orientations and intermolecular interactions in a derivative of pyrene on its supramolecular self-assembly in solution has been investigated using quantum chemical and force field based computational approaches. Five possible dipole configurations of the molecule have been examined, among which the one in which adjacent dipole vectors are antiparallel to each other is determined to be the ground state, on electrostatic grounds. Self-assembly of this molecule under realistic conditions has been studied using MD simulations. Dipolar relaxation in its liquid crystalline (LC) phase has been investigated and contrasted against that in the well-established benzene-1,3,5-tricarboxamide (BTA) family. The dihedral barrier related to the amide dipole flip is larger in the pyrene system than in BTA which explains the differences in their dipolar relaxation behaviors. The mechanism underlying polarization switching upon the application of an external electric field in the LC phase is investigated. Unlike in BTA, this switching is not associated with a reversal of the helical sense of the hydrogen bonded chains, due to differences in molecular symmetry. The observations enable general conclusions on the relationship between electric field induced chiral enhancement and symmetry to be drawn.

Curvature effect on polarization of light emitted from chiral carbon nanotubes.

We investigate that effect of the curvature on induced hybridization and modification of emission profiles for each chiral's index single-wall carbon nanotubes (SWCNTs). According to the Schwinger two particle pair state method, we provide an analytical expression by calculating polar of spot intensity as a function of the polar angle. The emission profiles for indirect transition have an asymmetric shape as a function of the electron wave vector of the axis direction kt and depend on the chiral index. Here we show polarization-dependent, given analytically by expanding the matrix element into the scalar product of the light polarization vector and the dipole vector. These scalar products having a maximum value depend on the summation of phase factors of spinors of electrons in the conduction band Φc and valence band Φv. In the case of direct transition, dipole vector tube axis is maximum at the phase summation of Φc and Φv is 0 or 2π. In contrast, the maximum dipole vector circumference is obtained at the phase summation of π for the case of indirect transition. We can predict a strong emission peak and emission profiles which can be used to identify optical transitions in an individual SWCNT with different chiral indices experimentally.

The Molecular Origin of Anisotropic Emission in an Organic Light-Emitting Diode.

Atomistic nonequilibrium molecular dynamics simulations have been used to model the induction of molecular orientation anisotropy within the emission layer of an organic light-emitting diode (OLED) formed by vapor deposition. Two emitter species were compared: racemic fac-tris(2-phenylpyridine)iridium(III) (Ir(ppy)3) and trans-bis(2-phenylpyridine)(acetylacetonate)iridium(III) (Ir(ppy)2(acac)). The simulations show that the molecular symmetry axes of both emitters preferentially align perpendicular to the surface during deposition. The molecular arrangement formed on deposition combined with consideration of the transition dipole moments provides insight into experimental reports that Ir(ppy)3 shows isotropic emission, while Ir(ppy)2(acac) displays improved efficiency due to an apparent preferential alignment of the transition dipole vectors parallel to the substrate. The simulations indicate that this difference is not due to differences in the extent of emitter alignment, but rather differences in the direction of the transition dipoles within the two complexes.

Directionality of Cation/Molecule Bonding in Lewis Bases Containing the Carbonyl Group.

Relationship between the C═O-X+ (X = H, Li, Na, K, Al, Cu) angle and covalent characteristic of the X+-M (M = CH2O, CH3CHO, acetone, imidazol-2-one (C2H2N2O), cytosine, γ-butyrolactone) was investigated, theoretically. The calculated electron densities ρ at the bond critical points revealed that the covalency of the M-X+ interaction depended on the nature of the cation and varied as H+ > Cu+ > Al+ > Li+ > Na+ > K+. The alkali cations tended to participate in electrostatic interactions and aligned with the direction of the molecule dipole or local dipole of C═O group to form linear C═O-X geometries. Because of overlapping with lone-pair electrons of the sp2 carbonyl oxygen, the H+ and Cu+ formed a bent C═O-X angle. Al+ displayed an intermediate behavior; the C═O-Al angle was 180° in [CH2O/Al]+ (mainly electrostatic), but when the angle was bent (146°) under the effect of local dipole of an adjacent imine group in cytosine, the covalency of the CO-Al+ interaction increased. The C═O-X angles in M/X+ adduct ions were scanned in different O-X bond lengths. It was found that the most favorable C═O-X angle depended on the O-X bond length. This dependency was attributed to variation of covalent and electrostatic contributions with O-X distance. In addition, the structures of [CH2S/X]+ and [CH2Se/X]+ were studied, and only bent C═S-X and C═Se-X angles were obtained for all cations, although the dipole vectors of CH2S and CH2Se coincide with the C═S and C═Se bonds. The bending of the C═S-X and C═Se-X angles was attributed to the covalent characteristic of S-X and Se-X interactions due to high polarizability of S and Se atoms.

Plasmonic Purcell effect reveals obliquely ordered phosphorescent emitters in Organic LEDs

The non-isotropic alignment of molecules can increase the interaction efficiency with propagating light fields. This applies to both emissive and absorptive systems and can be exploited for achieving unprecedented efficiencies of organic opto-electronic devices such as organic light-emitting diodes. Optical analysis has revealed certain phosphorescent emitters to align spontaneously in an advantageous orientation. Unfortunately, established approaches only determine an average orientation because emission patterns solely depend on the second moments of the transition dipole vector distribution. In order to resolve further details of such a distribution, additional differences in the emission characteristics of parallel and perpendicularly oriented emitters need to be introduced. A thin metal layer near the emitters introduces plasmon mediated losses mostly for perpendicular emitters. Then, analyzing the emission at different polarizations allows one to measure emission lifetimes of mostly parallel or mostly perpendicular oriented emitters. This should alter the transient emission when observing the temporal phosphorescence decay under different directions and/or polarizations. The angular width of the orientation distribution can be derived from the degree of such lifetime splitting. Our results suggest a narrow but obliquely oriented molecular ensemble of Ir(MDQ)2(acac) doped into the α-NPD host inside an Organic LED stack.

Highly Anisotropic in-Plane Excitons in Atomically Thin and Bulklike 1T'-ReSe2.

Atomically thin materials such as graphene or MoS2 are of high in-plane symmetry. Crystals with reduced symmetry hold the promise for novel optoelectronic devices based on their anisotropy in current flow or light polarization. Here, we present polarization-resolved optical transmission and photoluminescence spectroscopy of excitons in 1T'-ReSe2. On reducing the crystal thickness from bulk to a monolayer, we observe a strong blue shift of the optical band gap from 1.37 to 1.50 eV. The excitons are strongly polarized with dipole vectors along different crystal directions, which persist from bulk down to monolayer thickness. The experimental results are well reproduced by ab initio calculations based on the GW-BSE approach within LDA+GdW approximation. The excitons have high binding energies of 860 meV for the monolayer and 120 meV for bulk. They are strongly confined within a single layer even for the bulk crystal. In addition, we find in our calculations a direct band gap in 1T'-ReSe2 regardless of crystal thickness, indicating weak interlayer coupling effects on the band gap characteristics. Our results pave the way for polarization-sensitive applications, such as optical logic circuits operating in the infrared spectral region.

Colloidal Synthesis of CH3 NH3 PbBr3 Nanoplatelets with Polarized Emission through Self-Organization.

We report a combined experimental and theoretical study of the synthesis of CH3 NH3 PbBr3 nanoplatelets through self-organization. Shape transformation from spherical nanodots to square or rectangular nanoplatelets can be achieved by keeping the preformed colloidal nanocrystals at a high concentration (3.5 mg mL-1 ) for 3 days, or combining the synthesis of nanodots with self-organization. The average thickness of the resulting CH3 NH3 PbBr3 nanoplatelets is similar to the size of the original nanoparticles, and we also noticed several nanoplatelets with circular or square holes, suggesting that the shape transformation experienced a self-organization process through dipole-dipole interactions along with a realignment of dipolar vectors. Additionally, the CH3 NH3 PbBr3 nanoplatelets exhibit excellent polarized emissions for stretched CH3 NH3 PbBr3 nanoplatelets embedded in a polymer composite film, showing advantageous photoluminescence properties for display backlights.

Colloidal Synthesis of CH3NH3PbBr3 Nanoplatelets with Polarized Emission through Self‐Organization

AbstractWe report a combined experimental and theoretical study of the synthesis of CH3NH3PbBr3 nanoplatelets through self‐organization. Shape transformation from spherical nanodots to square or rectangular nanoplatelets can be achieved by keeping the preformed colloidal nanocrystals at a high concentration (3.5 mg mL−1) for 3 days, or combining the synthesis of nanodots with self‐organization. The average thickness of the resulting CH3NH3PbBr3 nanoplatelets is similar to the size of the original nanoparticles, and we also noticed several nanoplatelets with circular or square holes, suggesting that the shape transformation experienced a self‐organization process through dipole–dipole interactions along with a realignment of dipolar vectors. Additionally, the CH3NH3PbBr3 nanoplatelets exhibit excellent polarized emissions for stretched CH3NH3PbBr3 nanoplatelets embedded in a polymer composite film, showing advantageous photoluminescence properties for display backlights.

Simulation study on the structural properties of colloidal particles with offset dipoles

A major research theme in materials science is determining how the self-assembly of new generations of colloidal particles of complex shape and surface charge is guided by their interparticle interactions. In this paper, we describe results from quasi-2D Monte Carlo simulations of systems of colloidal particles with offset transversely-oriented extended dipole-like charge distributions interacting via an intermediate-ranged Yukawa potential. The systems are cooled slowly through an annealing procedure during which the temperature is lowered in discrete steps, allowing the system to equilibrate. We perform ground state calculations for two, three and four particles at several shifts of the dipole vector from the particle center. We create state diagrams in the plane spanned by the temperature and the area fraction outlining the boundaries between fluid, string-fluid and percolated states at various values of the shift. Remarkably we find that the effective cooling rate in our simulations has an impact on the structures formed, with chains being more prevalent if the system is cooled quickly and cyclic structures more prevalent if the system is cooled slowly. As the dipole is further shifted from the center, there is an increased tendency to assemble into small cyclic structures at intermediate temperatures. These systems further self-assemble into open lattice-like arrangements at very low temperatures. The novel structures identified might be useful for photonic applications, new types of porous media for filtration and catalysis, and gel matrices with unusual properties.

Effects of electric field on thermodynamics and ordering of a dipolar liquid.

We propose that an electric field's role in changing the structural disorder may be investigated by comparing the field-induced entropy decrease, ΔES, against the pressure-induced and cooling-induced entropy decreases, ΔpS and ΔTS, respectively, for the same increase in the dielectric α-relaxation time, Δτα, or in the viscosity. If these three quantities are found to be the same, the change in the number of microstates, Δln Ω = ΔS/R, would be the same whether there is an electric field-induced dipole vector alignment, or not. The available data [S. Samanta and R. Richert, J. Chem. Phys. 142, 044504 (2015)] show that ΔES ≅ ΔpS, and ΔES ≅ ΔTS. We further argue that in the case of conformational disorder without hydrodynamics, as for a flexible molecule's orientationally disordered or plastic crystal, ΔTS would be more negative than ΔES for the same increase in Δτα. For cyclo-octanol plastic crystal, whose octyl-ring would lose some of its dielectrically inactive conformational degrees of freedom on cooling, ΔTS is five-times ΔES. Hence the entropy of such crystals may not be related to their τα, an aspect relevant to certain biopolymer crystals. We also mention other effects of E. The findings are relevant to a number of recent studies on the analysis of the effect of electric field on a liquid's properties. The method can be used to study the role of other entropy-altering variables in liquid crystals and ferromagnetic liquids.

Stochastic reversal dynamics of two interacting magnetic dipoles: A simple model experiment.

We report an experimental study of the dynamics of two coupled magnetic dipoles. The experiment consists in two coplanar permanent disk magnets separated by a distance d, each allowed to rotate on a fixed parallel axis-each magnet's axis being perpendicular to its dipolar moment vector. A torque of adjustable strength can be externally applied to one of the magnets, the other magnet being free. The driving torque may be time-independent or temporally fluctuating. We study the influence of the parameters of the driving torque on the dynamics of the coupled system, in particular the emergence of dynamical regimes such as stochastic reversals. We report transitions between stationary and stochastic reversal regimes. All the observed features can be understood by a simple mechanical dynamical model. The transition between statistically stationary regimes and reversals is explained introducing an effective potential energy incorporating both the coupling between magnets and the external driving. Relations between this simple experimental model with macroscopic models of magnetic spin coupling, as well as with chaotic reversals of turbulent dynamos, are discussed.

Sharp Toroidal Resonances in Planar Terahertz Metasurfaces.

A toroidal dipole in metasurfaces provides an alternate approach for the excitation of high-Q resonances. In contrast to conventional multipoles, the toroidal dipole interaction strength depends on the time derivative of the surrounding electric field. A characteristic feature of toroidal dipoles is tightly confined loops of oscillating magnetic field that curl around the fictitious arrow of the toroidal dipole vector.

Molecular Dipole Moments within the Incremental Scheme Using the Domain-Specific Basis-Set Approach.

We present the first implementation of the fully automated incremental scheme for CCSD unrelaxed dipole moments using the domain-specific basis-set approach. Truncation parameters are varied, and the accuracy of the method is statistically analyzed for a test set of 20 molecules. The local approximations introduce small errors at second order and negligible ones at third order. For a third-order incremental CCSD expansion with a CC2 error correction, a cc-pVDZ/SV domain-specific basis set (tmain = 3.5 Bohr), and the truncation parameter f = 30 Bohr, we obtain a mean error of 0.00 mau (-0.20 mau) and a standard deviation of 1.95 mau (2.17 mau) for the total dipole moments (Cartesian components of the dipole vectors). By analyzing incremental CCSD energies, we demonstrate that the MP2 and CC2 error correction schemes are an exclusive correction for the domain-specific basis-set error. Our implementation of the incremental scheme provides fully automated computations of highly accurate dipole moments at reduced computational cost and is fully parallelized in terms of the calculation of the increments. Therefore, one can utilize the incremental scheme, on the same hardware, to extend the basis set in comparison to standard CCSD and thus obtain a better total accuracy.

Photon energy dependence of angle-resolved photoemission spectroscopy in graphene

The photon energy dependence of angle-resolved photoemission spectroscopy (ARPES) in graphene is investigated experimentally and theoretically. By applying light with energy of around $46\phantom{\rule{0.28em}{0ex}}\phantom{\rule{0.28em}{0ex}}\mathrm{eV}$, we found an unexpected increase in the ARPES relative intensity of graphene for the $p$ branch (ARPES spectra brightened by the $p$-polarized light) with respect to the $s$ branch (those brightened by the $s$-polarized light). The origin of the enhanced $p$-branch intensity is explained by first-principles calculations, in which we show (1) the optical dipole vector as a function of final-state energies of the excited electron, (2) the absorption intensity as a function of the incident light angle, and (3) the symmetry of the initial and the final states. The calculated results imply that the dipole vector of the excited electron near $46\phantom{\rule{0.28em}{0ex}}\phantom{\rule{0.28em}{0ex}}\mathrm{eV}$ has an exceptionally large component in the normal direction of the graphene surface compared to that within the graphene plane, which could be the main reason for the enhancement of the $p$-branch intensity.