Evidence for a dipolar-coupled AM system in carnosine in human calf muscle from in vivo 1H NMR spectroscopy

NASA Astrophysics Data System (ADS)

Schröder, Leif; Bachert, Peter

2003-10-01

Spin systems with residual dipolar couplings such as creatine, taurine, and lactate in skeletal muscle tissue exhibit first-order spectra in in vivo 1H NMR spectroscopy at 1.5 T because the coupled protons are represented by (nearly) symmetrized eigenfunctions. The imidazole ring protons (H2, H4) of carnosine are suspected to form also a coupled system. The ring's stiffness could enable a connectivity between these anisochronous protons with the consequence of second-order spectra at low field strength. Our purpose was to study whether this deviation from the Paschen-Back condition can be used to detect the H2-H4 coupling in localized 1D 1H NMR spectra obtained at 1.5 T (64 MHz) from the human calf in a conventional whole-body scanner. As for the hydrogen hyperfine interaction, a Breit-Rabi equation was derived to describe the transition from Zeeman to Paschen-Back regime for two dipolar-coupled protons. The ratio of the measurable coupling strength ( Sk) and the difference in resonance frequencies of the coupled spins (Δ ω) induces quantum-state mixing of various degree upon definition of an appropriate eigenbase of the coupled spin system. The corresponding Clebsch-Gordan coefficients manifest in characteristic energy corrections in the Breit-Rabi formula. These additional terms were used to define an asymmetry parameter of the line positions as a function of Sk and Δ ω. The observed frequency shifts of the resonances were found to be consistent with this parameter within the accuracy achievable in in vivo NMR spectroscopy. Thus it was possible to identify the origin of satellite peaks of H2, H4 and to describe this so far not investigated type of residual dipolar coupling in vivo.

Modeling helical proteins using residual dipolar couplings, sparse long-range distance constraints and a simple residue-based force field

PubMed Central

Eggimann, Becky L.; Vostrikov, Vitaly V.; Veglia, Gianluigi; Siepmann, J. Ilja

2013-01-01

We present a fast and simple protocol to obtain moderate-resolution backbone structures of helical proteins. This approach utilizes a combination of sparse backbone NMR data (residual dipolar couplings and paramagnetic relaxation enhancements) or EPR data with a residue-based force field and Monte Carlo/simulated annealing protocol to explore the folding energy landscape of helical proteins. By using only backbone NMR data, which are relatively easy to collect and analyze, and strategically placed spin relaxation probes, we show that it is possible to obtain protein structures with correct helical topology and backbone RMS deviations well below 4 Å. This approach offers promising alternatives for the structural determination of proteins in which nuclear Overha-user effect data are difficult or impossible to assign and produces initial models that will speed up the high-resolution structure determination by NMR spectroscopy. PMID:24639619

A unified heteronuclear decoupling strategy for magic-angle-spinning solid-state NMR spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Equbal, Asif; Bjerring, Morten; Nielsen, Niels Chr., E-mail: madhu@tifr.res.in, E-mail: ncn@inano.au.dk

2015-05-14

A unified strategy of two-pulse based heteronuclear decoupling for solid-state magic-angle spinning nuclear magnetic resonance is presented. The analysis presented here shows that different decoupling sequences like two-pulse phase-modulation (TPPM), X-inverse-X (XiX), and finite pulse refocused continuous wave (rCW{sup A}) are basically specific solutions of a more generalized decoupling scheme which incorporates the concept of time-modulation along with phase-modulation. A plethora of other good decoupling conditions apart from the standard, TPPM, XiX, and rCW{sup A} decoupling conditions are available from the unified decoupling approach. The importance of combined time- and phase-modulation in order to achieve the best decoupling conditions ismore » delineated. The consequences of different indirect dipolar interactions arising from cross terms comprising of heteronuclear and homonuclear dipolar coupling terms and also those between heteronuclear dipolar coupling and chemical-shift anisotropy terms are presented in order to unfold the effects of anisotropic interactions under different decoupling conditions. Extensive numerical simulation results are corroborated with experiments on standard amino acids.« less

Relaxation dynamics of a driven two-level system coupled to a Bose-Einstein condensate: application to quantum dot-dipolar exciton gas hybrid systems.

PubMed

Kovalev, Vadim M; Tse, Wang-Kong

2017-11-22

We develop a microscopic theory for the relaxation dynamics of an optically pumped two-level system (TLS) coupled to a bath of weakly interacting Bose gas. Using Keldysh formalism and diagrammatic perturbation theory, expressions for the relaxation times of the TLS Rabi oscillations are derived when the boson bath is in the normal state and the Bose-Einstein condensate (BEC) state. We apply our general theory to consider an irradiated quantum dot coupled with a boson bath consisting of a two-dimensional dipolar exciton gas. When the bath is in the BEC regime, relaxation of the Rabi oscillations is due to both condensate and non-condensate fractions of the bath bosons for weak TLS-light coupling and pre dominantly due to the non-condensate fraction for strong TLS-light coupling. Our theory also shows that a phase transition of the bath from the normal to the BEC state strongly influences the relaxation rate of the TLS Rabi oscillations. The TLS relaxation rate is approximately independent of the pump field frequency and monotonically dependent on the field strength when the bath is in the low-temperature regime of the normal phase. Phase transition of the dipolar exciton gas leads to a non-monotonic dependence of the TLS relaxation rate on both the pump field frequency and field strength, providing a characteristic signature for the detection of BEC phase transition of the coupled dipolar exciton gas.

Coherent manipulation of dipolar coupled spins in an anisotropic environment

NASA Astrophysics Data System (ADS)

Baibekov, E. I.; Gafurov, M. R.; Zverev, D. G.; Kurkin, I. N.; Malkin, B. Z.; Barbara, B.

2014-11-01

We study coherent dynamics in a system of dipolar coupled spin qubits diluted in a solid and subjected to a driving microwave field. In the case of rare earth ions, an anisotropic crystal background results in anisotropic g tensor and thus modifies the dipolar coupling. We develop a microscopic theory of spin relaxation in a transient regime for the frequently encountered case of axially symmetric crystal field. The calculated decoherence rate is nonlinear in the Rabi frequency. We show that the direction of a static magnetic field that corresponds to the highest spin g factor is preferable in order to obtain a higher number of coherent qubit operations. The results of calculations are in excellent agreement with our experimental data on Rabi oscillations recorded for a series of CaW O4 crystals with different concentrations of N d3 + ions.

Measurement of untruncated nuclear spin interactions via zero- to ultralow-field nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Blanchard, J. W.; Sjolander, T. F.; King, J. P.; Ledbetter, M. P.; Levine, E. H.; Bajaj, V. S.; Budker, D.; Pines, A.

2015-12-01

Zero- to ultralow-field nuclear magnetic resonance (ZULF NMR) provides a new regime for the measurement of nuclear spin-spin interactions free from the effects of large magnetic fields, such as truncation of terms that do not commute with the Zeeman Hamiltonian. One such interaction, the magnetic dipole-dipole coupling, is a valuable source of spatial information in NMR, though many terms are unobservable in high-field NMR, and the coupling averages to zero under isotropic molecular tumbling. Under partial alignment, this information is retained in the form of so-called residual dipolar couplings. We report zero- to ultralow-field NMR measurements of residual dipolar couplings in acetonitrile-2-13C aligned in stretched polyvinyl acetate gels. This permits the investigation of dipolar couplings as a perturbation on the indirect spin-spin J coupling in the absence of an applied magnetic field. As a consequence of working at zero magnetic field, we observe terms of the dipole-dipole coupling Hamiltonian that are invisible in conventional high-field NMR. This technique expands the capabilities of zero- to ultralow-field NMR and has potential applications in precision measurement of subtle physical interactions, chemical analysis, and characterization of local mesoscale structure in materials.

NMR Detection Using Laser-Polarized Xenon as a DipolarSensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Granwehr, Josef; Urban, Jeffry T.; Trabesinger, Andreas H.

2005-02-28

Hyperpolarized Xe-129 can be used as a sensor to indirectly detect NMR spectra of heteronuclei that are neither covalently bound nor necessarily in direct contact with the Xe atoms, but coupled through long-range intermolecular dipolar couplings. In order to reintroduce long-range dipolar couplings the sample symmetry has to be broken. This can be done either by an asymmetric sample arrangement, or by breaking the symmetry of the spin magnetization with field gradient pulses. Experiments are performed where only a small fraction of the available Xe-129 magnetization is used for each point, so that a single batch of xenon suffices formore » the point-by-point acquisition of a heteronuclear NMR spectrum. Examples with H-1 as analyte nucleus show that these methods have the potential to obtain spectra with a resolution that is high enough to determine homonuclear J couplings. The applicability of this technique with remote detection is discussed.« less

Nuclear magnetic relaxation by the dipolar EMOR mechanism: General theory with applications to two-spin systems.

PubMed

Chang, Zhiwei; Halle, Bertil

2016-02-28

In aqueous systems with immobilized macromolecules, including biological tissue, the longitudinal spin relaxation of water protons is primarily induced by exchange-mediated orientational randomization (EMOR) of intra- and intermolecular magnetic dipole-dipole couplings. We have embarked on a systematic program to develop, from the stochastic Liouville equation, a general and rigorous theory that can describe relaxation by the dipolar EMOR mechanism over the full range of exchange rates, dipole coupling strengths, and Larmor frequencies. Here, we present a general theoretical framework applicable to spin systems of arbitrary size with symmetric or asymmetric exchange. So far, the dipolar EMOR theory is only available for a two-spin system with symmetric exchange. Asymmetric exchange, when the spin system is fragmented by the exchange, introduces new and unexpected phenomena. Notably, the anisotropic dipole couplings of non-exchanging spins break the axial symmetry in spin Liouville space, thereby opening up new relaxation channels in the locally anisotropic sites, including longitudinal-transverse cross relaxation. Such cross-mode relaxation operates only at low fields; at higher fields it becomes nonsecular, leading to an unusual inverted relaxation dispersion that splits the extreme-narrowing regime into two sub-regimes. The general dipolar EMOR theory is illustrated here by a detailed analysis of the asymmetric two-spin case, for which we present relaxation dispersion profiles over a wide range of conditions as well as analytical results for integral relaxation rates and time-dependent spin modes in the zero-field and motional-narrowing regimes. The general theoretical framework presented here will enable a quantitative analysis of frequency-dependent water-proton longitudinal relaxation in model systems with immobilized macromolecules and, ultimately, will provide a rigorous link between relaxation-based magnetic resonance image contrast and molecular parameters.

Nuclear magnetic relaxation by the dipolar EMOR mechanism: General theory with applications to two-spin systems

NASA Astrophysics Data System (ADS)

Chang, Zhiwei; Halle, Bertil

2016-02-01

In aqueous systems with immobilized macromolecules, including biological tissue, the longitudinal spin relaxation of water protons is primarily induced by exchange-mediated orientational randomization (EMOR) of intra- and intermolecular magnetic dipole-dipole couplings. We have embarked on a systematic program to develop, from the stochastic Liouville equation, a general and rigorous theory that can describe relaxation by the dipolar EMOR mechanism over the full range of exchange rates, dipole coupling strengths, and Larmor frequencies. Here, we present a general theoretical framework applicable to spin systems of arbitrary size with symmetric or asymmetric exchange. So far, the dipolar EMOR theory is only available for a two-spin system with symmetric exchange. Asymmetric exchange, when the spin system is fragmented by the exchange, introduces new and unexpected phenomena. Notably, the anisotropic dipole couplings of non-exchanging spins break the axial symmetry in spin Liouville space, thereby opening up new relaxation channels in the locally anisotropic sites, including longitudinal-transverse cross relaxation. Such cross-mode relaxation operates only at low fields; at higher fields it becomes nonsecular, leading to an unusual inverted relaxation dispersion that splits the extreme-narrowing regime into two sub-regimes. The general dipolar EMOR theory is illustrated here by a detailed analysis of the asymmetric two-spin case, for which we present relaxation dispersion profiles over a wide range of conditions as well as analytical results for integral relaxation rates and time-dependent spin modes in the zero-field and motional-narrowing regimes. The general theoretical framework presented here will enable a quantitative analysis of frequency-dependent water-proton longitudinal relaxation in model systems with immobilized macromolecules and, ultimately, will provide a rigorous link between relaxation-based magnetic resonance image contrast and molecular parameters.

Sensitivity-enhanced IPAP experiments for measuring one-bond 13C '- 13C α and 13C α- 1H α residual dipolar couplings in proteins

NASA Astrophysics Data System (ADS)

Ding, Keyang; Gronenborn, Angela M.

2004-04-01

Sensitivity-enhanced 2D IPAP experiments using the accordion principle for measuring one-bond 13C '- 13C α and 1H α- 13C α dipolar couplings in proteins are presented. The resolution of the resulting spectra is identical to that of the decoupled HSQC spectra and the sensitivity of the corresponding 1D acquisitions are only slightly lower than those obtained with 3D HNCO and 3D HN(COCA)HA pulse sequences due to an additional delay 2 Δ. For cases of limited resolution in the 2D 15N- 1H N HSQC spectrum the current pulse sequences can easily be modified into 3D versions by introducing a poorly digitized third dimension, if so desired. The experiments described here are a valuable addition to the suites available for determination of residual dipolar couplings in biological systems.

Spin-orbit-coupled Bose-Einstein condensates of rotating polar molecules

NASA Astrophysics Data System (ADS)

Deng, Y.; You, L.; Yi, S.

2018-05-01

An experimental proposal for realizing spin-orbit (SO) coupling of pseudospin 1 in the ground manifold 1Σ (υ =0 ) of (bosonic) bialkali polar molecules is presented. The three spin components are composed of the ground rotational state and two substates from the first excited rotational level. Using hyperfine resolved Raman processes through two select excited states resonantly coupled by a microwave, an effective coupling between the spin tensor and linear momentum is realized. The properties of Bose-Einstein condensates for such SO-coupled molecules exhibiting dipolar interactions are further explored. In addition to the SO-coupling-induced stripe structures, the singly and doubly quantized vortex phases are found to appear, implicating exciting opportunities for exploring novel quantum physics using SO-coupled rotating polar molecules with dipolar interactions.

Influence of anisotropic dipolar interaction on the spin dynamics of Ni80Fe20 nanodot arrays arranged in honeycomb and octagonal lattices

NASA Astrophysics Data System (ADS)

Mondal, Sucheta; Barman, Saswati; Choudhury, Samiran; Otani, Yoshichika; Barman, Anjan

2018-07-01

Ultrafast spin dynamics in ferromagnetic nanodot arrays with dot diameter 100 nm and thickness 20 nm arranged in honeycomb and octagonal lattice symmetries are studied to explore the tunability of the collective magnetization dynamics. By varying the inter-dot separation between 30 nm and 300 nm drastic variation in the precessional dynamics from strongly collective to completely isolated regime has been observed by using all-optical time-resolved magneto-optical Kerr microscope. Micromagnetic simulation is exploited to gain insights about the resonant mode profiles and magnetic coupling between the nanodots. A significant spectral and spatial variation in the resonant mode with increasing dipolar interaction is demonstrated with increasing inter-dot separation. The spins driven by effective field inside single nanodots are prone to precess independently, generating two self-standing centre and edge modes in the array that are influenced by the relative orientation between the inter-dot coupling direction and bias magnetic field. The anisotropic behavior of dipolar field is rigorously investigated here. Splitting of the centre mode in case of octagonal lattice is experimentally observed here as a consequence of the anisotropic dipolar field between the nanodot pairs coupled horizontally and vertically, which is not found in the honeycomb lattice. In addition, proper understanding of the modification of dynamic mode profile by neighboring dipolar interaction built up here, is imperative for further control of the dynamic dipolar interaction and the corresponding collective excitation in magnonic crystals. The usage of nanodot lattices with complex basis structures can be advantageous for the designing of high density magnetic recording media, spin-wave filter and logic devices.

Detection of magnetic dipolar coupling of water molecules at the nanoscale using quantum magnetometry

NASA Astrophysics Data System (ADS)

Yang, Zhiping; Shi, Fazhan; Wang, Pengfei; Raatz, Nicole; Li, Rui; Qin, Xi; Meijer, Jan; Duan, Changkui; Ju, Chenyong; Kong, Xi; Du, Jiangfeng

2018-05-01

It is a crucial issue to study interactions among water molecules and hydrophobic interfacial water at the nanoscale. Here we succeed in measuring the nuclear magnetic resonance spectrum of a diamond-water interfacial ice with a detection volume of about 2.2 ×10-22 L. More importantly, the magnetic dipolar coupling between the two protons of a water molecule is resolved by measuring the signal contributed from about 7000 water molecules at the nanoscale. The resolved intramolecule magnetic dipolar interactions are about 15 and 33 kHz with spectral resolution of 5 kHz. This work provides a platform for hydrophobic interfacial water study under ambient conditions, with further applications in more general nanoscale structural analysis.

NMR polarization echoes in a nematic liquid crystal

NASA Astrophysics Data System (ADS)

Levstein, Patricia R.; Chattah, Ana K.; Pastawski, Horacio M.; Raya, Jésus; Hirschinger, Jérôme

2004-10-01

We have modified the polarization echo (PE) sequence through the incorporation of Lee-Goldburg cross polarization steps to quench the 1H-1H dipolar dynamics. In this way, the 13C becomes an ideal local probe to inject and detect polarization in the proton system. This improvement made possible the observation of the local polarization P00(t) and polarization echoes in the interphenyl proton of the liquid crystal N-(4-methoxybenzylidene)-4-butylaniline. The decay of P00(t) was well fitted to an exponential law with a characteristic time τC≈310 μs. The hierarchy of the intramolecular dipolar couplings determines a dynamical bottleneck that justifies the use of the Fermi Golden Rule to obtain a spectral density consistent with the structural parameters. The time evolution of P00(t) was reversed by the PE sequence generating echoes at the time expected by the scaling of the dipolar Hamiltonian. This indicates that the reversible 1H-1H dipolar interaction is the main contribution to the local polarization decrease and that the exponential decay for P00(t) does not imply irreversibility. The attenuation of the echoes follows a Gaussian law with a characteristic time τφ≈527 μs. The shape and magnitude of the characteristic time of the PE decay suggest that it is dominated by the unperturbed homonuclear dipolar Hamiltonian. This means that τφ is an intrinsic property of the dipolar coupled network and not of other degrees of freedom. In this case, one cannot unambiguously identify the mechanism that produces the decoherence of the dipolar order. This is because even weak interactions are able to break the fragile multiple coherences originated on the dipolar evolution, hindering its reversal. Other schemes to investigate these underlying mechanisms are proposed.

Dynamics-based selective 2D 1H/1H chemical shift correlation spectroscopy under ultrafast MAS conditions

NASA Astrophysics Data System (ADS)

Zhang, Rongchun; Ramamoorthy, Ayyalusamy

2015-05-01

Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of 1H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of 1H/1H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials.

Conformational analysis of the anti-obesity drug lorcaserin in water: how to take advantage of long-range residual dipolar couplings.

PubMed

Trigo-Mouriño, Pablo; de la Fuente, M Carmen; Gil, Roberto R; Sánchez-Pedregal, Víctor M; Navarro-Vázquez, Armando

2013-10-25

The conformational state of 8-chloro-1-methyl-2,3,4,5-tetrahydro-1H-3-benzazepine hydrochloride (lorcaserin) in water has been determined on the basis of one-bond and long-range C-H residual dipolar coupling (RDC) data along with DFT computations and (3)J(HH) coupling-constant analysis. According to this analysis, lorcaserin exists as a conformational equilibrium of two crown-chair forms, of which the preferred conformation has the methyl group in an equatorial orientation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical study of homonuclear J coupling between quadrupolar spins: single-crystal, DOR, and J-resolved NMR.

PubMed

Perras, Frédéric A; Bryce, David L

2014-05-01

The theory describing homonuclear indirect nuclear spin-spin coupling (J) interactions between pairs of quadrupolar nuclei is outlined and supported by numerical calculations. The expected first-order multiplets for pairs of magnetically equivalent (A2), chemically equivalent (AA'), and non-equivalent (AX) quadrupolar nuclei are given. The various spectral changeovers from one first-order multiplet to another are investigated with numerical simulations using the SIMPSON program and the various thresholds defining each situation are given. The effects of chemical equivalence, as well as quadrupolar coupling, chemical shift differences, and dipolar coupling on double-rotation (DOR) and J-resolved NMR experiments for measuring homonuclear J coupling constants are investigated. The simulated J coupling multiplets under DOR conditions largely resemble the ideal multiplets predicted for single crystals, and a characteristic multiplet is expected for each of the A2, AA', and AX cases. The simulations demonstrate that it should be straightforward to distinguish between magnetic inequivalence and equivalence using J-resolved NMR, as was speculated previously. Additionally, it is shown that the second-order quadrupolar-dipolar cross-term does not affect the splittings in J-resolved experiments. Overall, the homonuclear J-resolved experiment for half-integer quadrupolar nuclei is demonstrated to be robust with respect to the effects of first- and second-order quadrupolar coupling, dipolar coupling, and chemical shift differences. Copyright © 2014 Elsevier Inc. All rights reserved.

Nuclear magnetic relaxation by the dipolar EMOR mechanism: Three-spin systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang, Zhiwei; Halle, Bertil, E-mail: bertil.halle@bpc.lu.se

2016-07-21

In aqueous systems with immobilized macromolecules, including biological tissue, the longitudinal spin relaxation of water protons is primarily induced by exchange-mediated orientational randomization (EMOR) of intra- and intermolecular magnetic dipole-dipole couplings. Starting from the stochastic Liouville equation, we have developed a non-perturbative theory that can describe relaxation by the dipolar EMOR mechanism over the full range of exchange rates, dipole couplings, and Larmor frequencies. Here, we implement the general dipolar EMOR theory for a macromolecule-bound three-spin system, where one, two, or all three spins exchange with the bulk solution phase. In contrast to the previously studied two-spin system with amore » single dipole coupling, there are now three dipole couplings, so relaxation is affected by distinct correlations as well as by self-correlations. Moreover, relaxation can now couple the magnetizations with three-spin modes and, in the presence of a static dipole coupling, with two-spin modes. As a result of this complexity, three secondary dispersion steps with different physical origins can appear in the longitudinal relaxation dispersion profile, in addition to the primary dispersion step at the Larmor frequency matching the exchange rate. Furthermore, and in contrast to the two-spin system, longitudinal relaxation can be significantly affected by chemical shifts and by the odd-valued (“imaginary”) part of the spectral density function. We anticipate that the detailed studies of two-spin and three-spin systems that have now been completed will provide the foundation for developing an approximate multi-spin dipolar EMOR theory sufficiently accurate and computationally efficient to allow quantitative molecular-level interpretation of frequency-dependent water-proton longitudinal relaxation data from biophysical model systems and soft biological tissue.« less

Limits in Proton Nuclear Singlet-State Lifetimes Measured with para-Hydrogen-Induced Polarization.

PubMed

Zhang, Yuning; Duan, Xueyou; Soon, Pei Che; Sychrovský, Vladimír; Canary, James W; Jerschow, Alexej

2016-10-05

The synthesis of a hyperpolarized molecule was developed, where the polarization and the singlet state were preserved over two controlled chemical steps. Nuclear singlet-state lifetimes close to 6 min for protons are reported in dimethyl fumarate. Owing to the high symmetry (AA'X 3 X 3 ' and A 2 systems), the singlet-state readout requires either a chemical desymmetrization or a long and repeated spin lock. Using DFT calculations and relaxation models, we further determine nuclear spin singlet lifetime limiting factors, which include the intramolecular dipolar coupling mechanism (proton-proton and proton-deuterium), the chemical shift anisotropy mechanism (symmetric and antisymmetric), and the intermolecular dipolar coupling mechanism (to oxygen and deuterium). If the limit of paramagnetic relaxation caused by residual oxygen could be lifted, the intramolecular dipolar coupling to deuterium would become the limiting relaxation mechanism and proton lifetimes upwards of 26 min could become available in the molecules considered here (dimethyl maleate and dimethyl fumarate). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase modulation in dipolar-coupled A 2 spin systems: effect of maximum state mixing in 1H NMR in vivo

NASA Astrophysics Data System (ADS)

Schröder, Leif; Schmitz, Christian; Bachert, Peter

2004-12-01

Coupling constants of nuclear spin systems can be determined from phase modulation of multiplet resonances. Strongly coupled systems such as citrate in prostatic tissue exhibit a more complex modulation than AX connectivities, because of substantial mixing of quantum states. An extreme limit is the coupling of n isochronous spins (A n system). It is observable only for directly connected spins like the methylene protons of creatine and phosphocreatine which experience residual dipolar coupling in intact muscle tissue in vivo. We will demonstrate that phase modulation of this "pseudo-strong" system is quite simple compared to those of AB systems. Theory predicts that the spin-echo experiment yields conditions as in the case of weak interactions, in particular, the phase modulation depends linearly on the line splitting and the echo time.

Excitonic energy transfer in light-harvesting complexes in purple bacteria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye Jun; Sun Kewei; Zhao Yang

Two distinct approaches, the Frenkel-Dirac time-dependent variation and the Haken-Strobl model, are adopted to study energy transfer dynamics in single-ring and double-ring light-harvesting (LH) systems in purple bacteria. It is found that the inclusion of long-range dipolar interactions in the two methods results in significant increase in intra- or inter-ring exciton transfer efficiency. The dependence of exciton transfer efficiency on trapping positions on single rings of LH2 (B850) and LH1 is similar to that in toy models with nearest-neighbor coupling only. However, owing to the symmetry breaking caused by the dimerization of BChls and dipolar couplings, such dependence has beenmore » largely suppressed. In the studies of coupled-ring systems, both methods reveal an interesting role of dipolar interactions in increasing energy transfer efficiency by introducing multiple intra/inter-ring transfer paths. Importantly, the time scale (4 ps) of inter-ring exciton transfer obtained from polaron dynamics is in good agreement with previous studies. In a double-ring LH2 system, non-nearest neighbor interactions can induce symmetry breaking, which leads to global and local minima of the average trapping time in the presence of a non-zero dephasing rate, suggesting that environment dephasing helps preserve quantum coherent energy transfer when the perfect circular symmetry in the hypothetic system is broken. This study reveals that dipolar coupling between chromophores may play an important role in the high energy transfer efficiency in the LH systems of purple bacteria and many other natural photosynthetic systems.« less

Attraction between Opposing Planar Dipolar Polymer Brushes

DOE PAGES

Mahalik, J. P.; Sumpter, Bobby G.; Kumar, Rajeev

2017-08-01

In this paper, we use a field theory approach to study the effects of permanent dipoles on interpenetration and free energy changes as a function of distance between two identical planar polymer brushes. Melts (i.e., solvent-free) and solvated brushes made up of polymers grafted on nonadsorbing substrates are studied. In particular, the weak coupling limit of the dipolar interactions is considered, which leads to concentration-dependent pairwise interactions, and the effects of orientational order are neglected. It is predicted that a gradual increase in the dipole moment of the polymer segments can lead to attractive interactions between the brushes at intermediatemore » separation distances. Finally, because classical theory of polymer brushes based on the strong stretching limit (SSL) and the standard self-consistent field theory (SCFT) simulations using the Flory’s χ parameter always predicts repulsive interactions at all separations, our work highlights the importance of dipolar interactions in tailoring and accurately predicting forces between polar polymeric interfaces in contact with each other.« less

Refocused continuous-wave decoupling: a new approach to heteronuclear dipolar decoupling in solid-state NMR spectroscopy.

PubMed

Vinther, Joachim M; Nielsen, Anders B; Bjerring, Morten; van Eck, Ernst R H; Kentgens, Arno P M; Khaneja, Navin; Nielsen, Niels Chr

2012-12-07

A novel strategy for heteronuclear dipolar decoupling in magic-angle spinning solid-state nuclear magnetic resonance (NMR) spectroscopy is presented, which eliminates residual static high-order terms in the effective Hamiltonian originating from interactions between oscillating dipolar and anisotropic shielding tensors. The method, called refocused continuous-wave (rCW) decoupling, is systematically established by interleaving continuous wave decoupling with appropriately inserted rotor-synchronized high-power π refocusing pulses of alternating phases. The effect of the refocusing pulses in eliminating residual effects from dipolar coupling in heteronuclear spin systems is rationalized by effective Hamiltonian calculations to third order. In some variants the π pulse refocusing is supplemented by insertion of rotor-synchronized π/2 purging pulses to further reduce the residual dipolar coupling effects. Five different rCW decoupling sequences are presented and their performance is compared to state-of-the-art decoupling methods. The rCW decoupling sequences benefit from extreme broadbandedness, tolerance towards rf inhomogeneity, and improved potential for decoupling at relatively low average rf field strengths. In numerical simulations, the rCW schemes clearly reveal superior characteristics relative to the best decoupling schemes presented so far, which we to some extent also are capable of demonstrating experimentally. A major advantage of the rCW decoupling methods is that they are easy to set up and optimize experimentally.

One-Shot Determination of Residual Dipolar Couplings: Application to the Structural Discrimination of Small Molecules Containing Multiple Stereocenters.

PubMed

Castañar, Laura; Garcia, Manuela; Hellemann, Erich; Nolis, Pau; Gil, Roberto R; Parella, Teodor

2016-11-18

A novel approach for the fast and efficient structural discrimination of molecules containing multiple stereochemical centers is described. A robust J-resolved HSQC experiment affording highly resolved 1 J CH / 1 T CH splittings along the indirect dimension and homodecoupled 1 H signals in the detected dimension is proposed. The experiment enables in situ distinction of both isotropic and anisotropic components of molecules dissolved in compressed PMMA gels, allowing a rapid and direct one-shot determination of accurate residual dipolar coupling constants from a single NMR spectrum.

Moderate MAS enhances local (1)H spin exchange and spin diffusion.

PubMed

Roos, Matthias; Micke, Peter; Saalwächter, Kay; Hempel, Günter

2015-11-01

Proton NMR spin-diffusion experiments are often combined with magic-angle spinning (MAS) to achieve higher spectral resolution of solid samples. Here we show that local proton spin diffusion can indeed become faster at low (<10 kHz) spinning rates as compared to static conditions. Spin diffusion under static conditions can thus be slower than the often referred value of 0.8 nm(2)/ms, which was determined using slow MAS (Clauss et al., 1993). The enhancement of spin diffusion by slow MAS relies on the modulation of the orientation-dependent dipolar couplings during sample rotation and goes along with transient level crossings in combination with dipolar truncation. The experimental finding and its explanation is supported by density matrix simulations, and also emphasizes the sensitivity of spin diffusion to the local coupling topology. The amplification of spin diffusion by slow MAS cannot be explained by any model based on independent spin pairs; at least three spins have to be considered. Copyright © 2015 Elsevier Inc. All rights reserved.

Magnetic Yoking and Tunable Interactions in FePt-Based Hard/Soft Bilayers

PubMed Central

Gilbert, Dustin A.; Liao, Jung-Wei; Kirby, Brian J.; Winklhofer, Michael; Lai, Chih-Huang; Liu, Kai

2016-01-01

Magnetic interactions in magnetic nanostructures are critical to nanomagnetic and spintronic explorations. Here we demonstrate an extremely sensitive magnetic yoking effect and tunable interactions in FePt based hard/soft bilayers mediated by the soft layer. Below the exchange length, a thin soft layer strongly exchange couples to the perpendicular moments of the hard layer; above the exchange length, just a few nanometers thicker, the soft layer moments turn in-plane and act to yoke the dipolar fields from the adjacent hard layer perpendicular domains. The evolution from exchange to dipolar-dominated interactions is experimentally captured by first-order reversal curves, the ΔM method, and polarized neutron reflectometry, and confirmed by micromagnetic simulations. These findings demonstrate an effective yoking approach to design and control magnetic interactions in wide varieties of magnetic nanostructures and devices. PMID:27604428

Quantum logic between remote quantum registers

NASA Astrophysics Data System (ADS)

Yao, N. Y.; Gong, Z.-X.; Laumann, C. R.; Bennett, S. D.; Duan, L.-M.; Lukin, M. D.; Jiang, L.; Gorshkov, A. V.

2013-02-01

We consider two approaches to dark-spin-mediated quantum computing in hybrid solid-state spin architectures. First, we review the notion of eigenmode-mediated unpolarized spin-chain state transfer and extend the analysis to various experimentally relevant imperfections: quenched disorder, dynamical decoherence, and uncompensated long-range coupling. In finite-length chains, the interplay between disorder-induced localization and decoherence yields a natural optimal channel fidelity, which we calculate. Long-range dipolar couplings induce a finite intrinsic lifetime for the mediating eigenmode; extensive numerical simulations of dipolar chains of lengths up to L=12 show remarkably high fidelity despite these decay processes. We further briefly consider the extension of the protocol to bosonic systems of coupled oscillators. Second, we introduce a quantum mirror based architecture for universal quantum computing that exploits all of the dark spins in the system as potential qubits. While this dramatically increases the number of qubits available, the composite operations required to manipulate dark-spin qubits significantly raise the error threshold for robust operation. Finally, we demonstrate that eigenmode-mediated state transfer can enable robust long-range logic between spatially separated nitrogen-vacancy registers in diamond; disorder-averaged numerics confirm that high-fidelity gates are achievable even in the presence of moderate disorder.

Conformational distribution of n-hexane in a nematic liquid crystal obtained from nuclear spin dipolar couplings by Monte Carlo sampling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luzar, M.; Rosen, M.E.; Caldarelli, S.

Motionally averaged proton-proton dipolar couplings measured by nuclear magnetic resonance (NMR) spectroscopy can provide information about the conformations and orientations sampled by partially oriented molecules. In this study, the measured dipolar couplings between pairs of protons on n-hexane dissolved in a nematic liquid crystal solvent are used as constraints in a Monte Carlo sampling of the conformations and orientations of n-hexane. Rotation about each carbon-carbon bond in the molecule is modeled by the complete sinusoidal torsional potential of Ryckaert and Bellemans rather than by the three-state rotational isomeric states (RIS) model that has been used in previous studies. Comparison ofmore » the results of the simulations using the Ryckaert-Bellemans potential and the RIS model indicates little difference in the values of the adjustable parameters and the quality of the fits to the experimental data. The primary difference between the models appears in the calculated conformer probability distributions for n-hexane, highlighting the importance of the exact shape of the torsional potential used to model carbon-carbon bond rotation in organic molecules. 23 refs., 3 figs., 4 tabs.« less

Near-field spatial mapping of strongly interacting multiple plasmonic infrared antennas.

PubMed

Grefe, Sarah E; Leiva, Daan; Mastel, Stefan; Dhuey, Scott D; Cabrini, Stefano; Schuck, P James; Abate, Yohannes

2013-11-21

Near-field dipolar plasmon interactions of multiple infrared antenna structures in the strong coupling limit are studied using scattering-type scanning near-field optical microscope (s-SNOM) and theoretical finite-difference time-domain (FDTD) calculations. We monitor in real-space the evolution of plasmon dipolar mode of a stationary antenna structure as multiple resonantly matched dipolar plasmon particles are closely approaching it. Interparticle separation, length and polarization dependent studies show that the cross geometry structure favors strong interparticle charge-charge, dipole-dipole and charge-dipole Coulomb interactions in the nanometer scale gap region, which results in strong field enhancement in cross-bowties and further allows these structures to be used as polarization filters. The nanoscale local field amplitude and phase maps show that due to strong interparticle Coulomb coupling, cross-bowtie structures redistribute and highly enhance the out-of-plane (perpendicular to the plane of the sample) plasmon near-field component at the gap region relative to ordinary bowties.

Molecular dynamics and information on possible sites of interaction of intramyocellular metabolites in vivo from resolved dipolar couplings in localized 1H NMR spectra

NASA Astrophysics Data System (ADS)

Schröder, Leif; Schmitz, Christian; Bachert, Peter

2004-12-01

Proton NMR resonances of the endogenous metabolites creatine and phosphocreatine ((P)Cr), taurine (Tau), and carnosine (Cs, β-alanyl- L-histidine) were studied with regard to residual dipolar couplings and molecular mobility. We present an analysis of the direct 1H- 1H interaction that provides information on motional reorientation of subgroups in these molecules in vivo. For this purpose, localized 1H NMR experiments were performed on m. gastrocnemius of healthy volunteers using a 1.5-T clinical whole-body MR scanner. We evaluated the observable dipolar coupling strength SD0 ( S = order parameter) of the (P)Cr-methyl triplet and the Tau-methylene doublet by means of the apparent line splitting. These were compared to the dipolar coupling strength of the (P)Cr-methylene doublet. In contrast to the aliphatic protons of (P)Cr and Tau, the aromatic H2 ( δ = 8 ppm) and H4 ( δ = 7 ppm) protons of the imidazole ring of Cs exhibit second-order spectra at 1.5 T. This effect is the consequence of incomplete transition from Zeeman to Paschen-Back regime and allows a determination of SD0 from H2 and H4 of Cs as an alternative to evaluating the multiplet splitting which can be measured directly in high-resolution 1H NMR spectra. Experimental data showed striking differences in the mobility of the metabolites when the dipolar coupling constant D0 (calculated with the internuclear distance known from molecular geometry in the case of complete absence of molecular dynamics and motion) is used for comparison. The aliphatic signals involve very small order parameters S ≈ (1.4 - 3) × 10 -4 indicating rapid reorientation of the corresponding subgroups in these metabolites. In contrast, analysis of the Cs resonances yielded S ≈ (113 - 137) × 10 -4. Thus, the immobilization of the Cs imidazole ring owing to an anisotropic cellular substructure in human m. gastrocnemius is much more effective than for (P)Cr and Tau subgroups. Furthermore, 1H NMR experiments on aqueous model solutions of histidine and N-acetyl- L-aspartate (NAA) enabled the assignment of an additional signal component at δ = 8 ppm of Cs in vivo to the amide group at the peptide bond. The visibility of this proton could result from hydrogen bonding which would agree with the anticipated stronger motional restriction of Cs. Referring to the observation that all dipolar-coupled multiplets resolved in localized in vivo 1H NMR spectra of human m. gastrocnemius collapse simultaneously when the fibre structure is tilted towards the magic angle ( θ ≈ 55°), a common model for molecular confinement in muscle tissue is proposed on the basis of an interaction of the studied metabolites with myocellular membrane phospholipids.

J-GFT NMR for precise measurement of mutually correlated nuclear spin-spin couplings.

PubMed

Atreya, Hanudatta S; Garcia, Erwin; Shen, Yang; Szyperski, Thomas

2007-01-24

G-matrix Fourier transform (GFT) NMR spectroscopy is presented for accurate and precise measurement of chemical shifts and nuclear spin-spin couplings correlated according to spin system. The new approach, named "J-GFT NMR", is based on a largely extended GFT NMR formalism and promises to have a broad impact on projection NMR spectroscopy. Specifically, constant-time J-GFT (6,2)D (HA-CA-CO)-N-HN was implemented for simultaneous measurement of five mutually correlated NMR parameters, that is, 15N backbone chemical shifts and the four one-bond spin-spin couplings 13Calpha-1Halpha, 13Calpha-13C', 15N-13C', and 15N-1HNu. The experiment was applied for measuring residual dipolar couplings (RDCs) in an 8 kDa protein Z-domain aligned with Pf1 phages. Comparison with RDC values extracted from conventional NMR experiments reveals that RDCs are measured with high precision and accuracy, which is attributable to the facts that (i) the use of constant time evolution ensures that signals do not broaden whenever multiple RDCs are jointly measured in a single dimension and (ii) RDCs are multiply encoded in the multiplets arising from the joint sampling. This corresponds to measuring the couplings multiple times in a statistically independent manner. A key feature of J-GFT NMR, i.e., the correlation of couplings according to spin systems without reference to sequential resonance assignments, promises to be particularly valuable for rapid identification of backbone conformation and classification of protein fold families on the basis of statistical analysis of dipolar couplings.

Polarized and asymmetric emission of single colloidal nanoplatelets (Conference Presentation)

NASA Astrophysics Data System (ADS)

Feng, Fu; N'Guyen, Thu Loan; Nasilowski, Michel; Lethiec, Clotilde M.; Dubertret, Benoit; Coolen, Laurent; Maître, Agnès.

2017-02-01

Efficient coupling of nanoemitters to photonic or plasmonic structures requires the control of the orientation of the emitting dipoles. Nevertheless controlling the dipole orientation remains an experimental challenge. Many experiments rely on the realization of numerous samples, in order to be able to statistically get a well aligned dipole to realize an efficient coupling to a nanostructure. In order to avoid these statistical trials, the knowledge of the nature of the emitter and its orientation is crucial for a deterministical approach. We developed a method [1],[2] relying on the combination of polarimetric measurement and emission diagram which gives fine information both on the emitting dipolar transition involved and on the dipolar orientation We analyse by this method square and rectangle single colloidal CdSe/CdS nanoplatetelets. We demonstrate that their emission can be described by just by two orthogonal dipoles lying in the plane of the platelets. More surprisingly the emission of the square nanoplatelets is not polarised whereas the rectangle one is. We demonstrate that this polarized emission is due to the rectangular shape anisotropy by a dielectric effect. [1] C. Lethiec, et al, Three-dimensional orientation measurement of a single fluorescent nanoemitter by polarization analysis, Phys. Rev. X 4, 021037 (2014), [2] C. Lethiec et al, Polarimetry-based analysis of dipolar transitions of single colloidal CdSe/CdS dot-inrods, New Journal of Physics 16, 093014 (2014) [3] S. Ithurria et al, colloidal nanoplatelets with 2 dimensional electronic structure, Nature Materials 10, 936 (2011)

Atom-Pair Kinetics with Strong Electric-Dipole Interactions.

PubMed

Thaicharoen, N; Gonçalves, L F; Raithel, G

2016-05-27

Rydberg-atom ensembles are switched from a weakly to a strongly interacting regime via adiabatic transformation of the atoms from an approximately nonpolar into a highly dipolar quantum state. The resultant electric dipole-dipole forces are probed using a device akin to a field ion microscope. Ion imaging and pair-correlation analysis reveal the kinetics of the interacting atoms. Dumbbell-shaped pair-correlation images demonstrate the anisotropy of the binary dipolar force. The dipolar C_{3} coefficient, derived from the time dependence of the images, agrees with the value calculated from the permanent electric-dipole moment of the atoms. The results indicate many-body dynamics akin to disorder-induced heating in strongly coupled particle systems.

Particle tracing modeling of ion fluxes at geosynchronous orbit

DOE PAGES

Brito, Thiago V.; Woodroffe, Jesse; Jordanova, Vania K.; ...

2017-10-31

The initial results of a coupled MHD/particle tracing method to evaluate particle fluxes in the inner magnetosphere are presented. This setup is capable of capturing the earthward particle acceleration process resulting from dipolarization events in the tail region of the magnetosphere. On the period of study, the MHD code was able to capture a dipolarization event and the particle tracing algorithm was able to capture our results of these disturbances and calculate proton fluxes in the night side geosynchronous orbit region. The simulation captured dispersionless injections as well as the energy dispersion signatures that are frequently observed by satellites atmore » geosynchronous orbit. Currently, ring current models rely on Maxwellian-type distributions based on either empirical flux values or sparse satellite data for their boundary conditions close to geosynchronous orbit. In spite of some differences in intensity and timing, the setup presented here is able to capture substorm injections, which represents an improvement regarding a reverse way of coupling these ring current models with MHD codes through the use of boundary conditions.« less

Particle tracing modeling of ion fluxes at geosynchronous orbit

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brito, Thiago V.; Woodroffe, Jesse; Jordanova, Vania K.

The initial results of a coupled MHD/particle tracing method to evaluate particle fluxes in the inner magnetosphere are presented. This setup is capable of capturing the earthward particle acceleration process resulting from dipolarization events in the tail region of the magnetosphere. On the period of study, the MHD code was able to capture a dipolarization event and the particle tracing algorithm was able to capture our results of these disturbances and calculate proton fluxes in the night side geosynchronous orbit region. The simulation captured dispersionless injections as well as the energy dispersion signatures that are frequently observed by satellites atmore » geosynchronous orbit. Currently, ring current models rely on Maxwellian-type distributions based on either empirical flux values or sparse satellite data for their boundary conditions close to geosynchronous orbit. In spite of some differences in intensity and timing, the setup presented here is able to capture substorm injections, which represents an improvement regarding a reverse way of coupling these ring current models with MHD codes through the use of boundary conditions.« less

(1)H-(13)C Hetero-nuclear dipole-dipole couplings of methyl groups in stationary and magic angle spinning solid-state NMR experiments of peptides and proteins.

PubMed

Wu, Chin H; Das, Bibhuti B; Opella, Stanley J

2010-02-01

(13)C NMR of isotopically labeled methyl groups has the potential to combine spectroscopic simplicity with ease of labeling for protein NMR studies. However, in most high resolution separated local field experiments, such as polarization inversion spin exchange at the magic angle (PISEMA), that are used to measure (1)H-(13)C hetero-nuclear dipolar couplings, the four-spin system of the methyl group presents complications. In this study, the properties of the (1)H-(13)C hetero-nuclear dipolar interactions of (13)C-labeled methyl groups are revealed through solid-state NMR experiments on a range of samples, including single crystals, stationary powders, and magic angle spinning of powders, of (13)C(3) labeled alanine alone and incorporated into a protein. The spectral simplifications resulting from proton detected local field (PDLF) experiments are shown to enhance resolution and simplify the interpretation of results on single crystals, magnetically aligned samples, and powders. The complementarity of stationary sample and magic angle spinning (MAS) measurements of dipolar couplings is demonstrated by applying polarization inversion spin exchange at the magic angle and magic angle spinning (PISEMAMAS) to unoriented samples. Copyright 2009 Elsevier Inc. All rights reserved.

Solid-state NMR detection of 14N-13C dipolar couplings between amino acid side groups provides constraints on amyloid fibril architecture.

PubMed

Middleton, David A

2011-02-01

Solid-state nuclear magnetic resonance (SSNMR) is a powerful technique for the structural analysis of amyloid fibrils. With suitable isotope labelling patterns, SSNMR can provide constraints on the secondary structure, alignment and registration of β-strands within amyloid fibrils and identify the tertiary and quaternary contacts defining the packing of the β-sheet layers. Detection of (14)N-(13)C dipolar couplings may provide potentially useful additional structural constraints on β-sheet packing within amyloid fibrils but has not until now been exploited for this purpose. Here a frequency-selective, transfer of population in double resonance SSNMR experiment is used to detect a weak (14)N-(13)C dipolar coupling in amyloid-like fibrils of the peptide H(2)N-SNNFGAILSS-COOH, which was uniformly (13)C and (15)N labelled across the four C-terminal amino acids. The (14)N-(13)C interatomic distance between leucine and asparagine side groups is constrained between 2.4 and 3.8 Å, which allows current structural models of the β-spine arrangement within the fibrils to be refined. This procedure could be useful for the general structural analysis of other proteins in condensed phases and environments, such as biological membranes. Copyright © 2011 John Wiley & Sons, Ltd.

Progressive Stereo Locking (PSL): A Residual Dipolar Coupling Based Force Field Method for Determining the Relative Configuration of Natural Products and Other Small Molecules.

PubMed

Cornilescu, Gabriel; Ramos Alvarenga, René F; Wyche, Thomas P; Bugni, Tim S; Gil, Roberto R; Cornilescu, Claudia C; Westler, William M; Markley, John L; Schwieters, Charles D

2017-08-18

Establishing the relative configuration of a bioactive natural product represents the most challenging part in determining its structure. Residual dipolar couplings (RDCs) are sensitive probes of the relative spatial orientation of internuclear vectors. We adapted a force field structure calculation methodology to allow free sampling of both R and S configurations of the stereocenters of interest. The algorithm uses a floating alignment tensor in a simulated annealing protocol to identify the conformations and configurations that best fit experimental RDC and distance restraints (from NOE and J-coupling data). A unique configuration (for rigid molecules) or a very small number of configurations (for less rigid molecules) of the structural models having the lowest chiral angle energies and reasonable magnitudes of the alignment tensor are provided as the best predictions of the unknown configuration. For highly flexible molecules, the progressive locking of their stereocenters into their statistically dominant R or S state dramatically reduces the number of possible relative configurations. The result is verified by checking that the same configuration is obtained by initiating the locking from different regions of the molecule. For all molecules tested having known configurations (with conformations ranging from mostly rigid to highly flexible), the method accurately determined the correct configuration.

Spin-correlated doublet pairs as intermediate states in charge separation processes

NASA Astrophysics Data System (ADS)

Kraffert, Felix; Behrends, Jan

2017-10-01

Spin-correlated charge-carrier pairs play a crucial role as intermediate states in charge separation both in natural photosynthesis as well as in solar cells. Using transient electron paramagnetic resonance (trEPR) spectroscopy in combination with spectral simulations, we study spin-correlated polaron pairs in polymer:fullerene blends as organic solar cells materials. The semi-analytical simulations presented here are based on the well-established theoretical description of spin-correlated radical pairs in biological systems, however, explicitly considering the disordered nature of polymer:fullerene blends. The large degree of disorder leads to the fact that many different relative orientations between both polarons forming the spin-correlated pairs have to be taken into account. This has important implications for the spectra, which differ significantly from those of spin-correlated radical pairs with a fixed relative orientation. We systematically study the influence of exchange and dipolar couplings on the trEPR spectra and compare the simulation results to measured X- and Q-band trEPR spectra. Our results demonstrate that assuming dipolar couplings alone does not allow us to reproduce the experimental spectra. Due to the rather delocalised nature of polarons in conjugated organic semiconductors, a significant isotropic exchange coupling needs to be included to achieve good agreement between experiments and simulations.

Multiscale simulations of defect dipole-enhanced electromechanical coupling at dilute defect concentrations

NASA Astrophysics Data System (ADS)

Liu, Shi; Cohen, R. E.

2017-08-01

The role of defects in solids of mixed ionic-covalent bonds such as ferroelectric oxides is complex. Current understanding of defects on ferroelectric properties at the single-defect level remains mostly at the empirical level, and the detailed atomistic mechanisms for many defect-mediated polarization-switching processes have not been convincingly revealed quantum mechanically. We simulate the polarization-electric field (P-E) and strain-electric field (ɛ-E) hysteresis loops for BaTiO3 in the presence of generic defect dipoles with large-scale molecular dynamics and provide a detailed atomistic picture of the defect dipole-enhanced electromechanical coupling. We develop a general first-principles-based atomistic model, enabling a quantitative understanding of the relationship between macroscopic ferroelectric properties and dipolar impurities of different orientations, concentrations, and dipole moments. We find that the collective orientation of dipolar defects relative to the external field is the key microscopic structure feature that strongly affects materials hardening/softening and electromechanical coupling. We show that a small concentration (≈0.1 at. %) of defect dipoles dramatically improves electromechanical responses. This offers the opportunity to improve the performance of inexpensive polycrystalline ferroelectric ceramics through defect dipole engineering for a range of applications including piezoelectric sensors, actuators, and transducers.

The physical mechanism of "inhomogeneous" magnetization transfer MRI

NASA Astrophysics Data System (ADS)

Manning, Alan P.; Chang, Kimberley L.; MacKay, Alex L.; Michal, Carl A.

2017-01-01

Inhomogeneous MT (ihMT) is a new magnetic resonance imaging technique that shows promise for myelin selectivity. Materials with a high proportion of lipids, such as white matter tissue, show a reduced intensity in magnetic resonance images acquired with selective prepulses at positive and negative offsets simultaneously compared to images with a single positive or negative offset prepulse of the same power. This effect was initially explained on the basis of hole-burning in inhomogeneously broadened lines of the lipid proton spin system. Our results contradict this explanation. ihMT in lipids can be understood with a simple spin-1 model of a coupled methylene proton pair. More generally, Provotorov theory can be used to consider the evolution of dipolar order in the non-aqueous spins during the prepulses. We show that the flip-angle dependence of the proton spectrum of a model lipid system (Prolipid-161) following dipolar order generation is in quantitative agreement with the model. In addition, we directly observe dipolar order and ihMT signals in the non-aqueous components of Prolipid-161 and homogeneously-broadened systems (hair, wood, and tendon) following ihMT prepulses. The observation of ihMT signals in tendon suggests that the technique may not be as specific to myelin as previously thought. Our work shows that ihMT occurs because of dipolar couplings alone, not from a specific type of spectral line broadening as its name suggests.

Overflow of a dipolar exciton trap at high magnetic fields

NASA Astrophysics Data System (ADS)

Dietl, Sebastian; Kowalik-Seidl, Katarzyna; Hammer, Lukas; Schuh, Dieter; Wegscheider, Werner; Holleitner, Alexander; Wurstbauer, Ursula

We study the photoluminescence of trapped dipolar excitons (IX) in coupled double GaAs quantum wells at low temperatures and high magnetic fields. A voltage-tunable electrode geometry controls the strength of the quantum confined Stark effect and defines the lateral trapping potential. Furthermore, it enhances the IX lifetime, enabling them to cool down to lattice temperature. We show that a magnetic field in Faraday configuration effectively prevents the escape of unbound photogenerated charge carriers from the trap area, thus increasing the density of dipolar excitons. For large magnetic fields, we observe an overflow of the IX trap and an effectively suppressed quantum confined Stark effect. We acknowledge financial support by the German Excellence Initiative via the Nanosystems Initiative Munich (NIM).

Efficient creation of dipolar coupled nitrogen-vacancy spin qubits in diamond

NASA Astrophysics Data System (ADS)

Jakobi, I.; Momenzadeh, S. A.; Fávaro de Oliveira, F.; Michl, J.; Ziem, F.; Schreck, M.; Neumann, P.; Denisenko, A.; Wrachtrup, J.

2016-09-01

Coherently coupled pairs or multimers of nitrogen-vacancy defect electron spins in diamond have many promising applications especially in quantum information processing (QIP) but also in nanoscale sensing applications. Scalable registers of spin qubits are essential to the progress of QIP. Ion implantation is the only known technique able to produce defect pairs close enough to allow spin coupling via dipolar interaction. Although several competing methods have been proposed to increase the resulting resolution of ion implantation, the reliable creation of working registers is still to be demonstrated. The current limitation are residual radiation-induced defects, resulting in degraded qubit performance as trade-off for positioning accuracy. Here we present an optimized estimation of nanomask implantation parameters that are most likely to produce interacting qubits under standard conditions. We apply our findings to a well-established technique, namely masks written in electron-beam lithography, to create coupled defect pairs with a reasonable probability. Furthermore, we investigate the scaling behavior and necessary improvements to efficiently engineer interacting spin architectures.

Quasi-one-dimensional spin-orbit- and Rabi-coupled bright dipolar Bose-Einstein-condensate solitons

NASA Astrophysics Data System (ADS)

Chiquillo, Emerson

2018-01-01

We study the formation of stable bright solitons in quasi-one-dimensional (quasi-1D) spin-orbit- (SO-) and Rabi-coupled two pseudospinor dipolar Bose-Einstein condensates (BECs) of 164Dy atoms in the presence of repulsive contact interactions. As a result of the combined attraction-repulsion effect of both interactions and the addition of SO and Rabi couplings, two kinds of ground states in the form of self-trapped bright solitons can be formed, a plane-wave soliton (PWS) and a stripe soliton (SS). These quasi-1D solitons cannot exist in a condensate with purely repulsive contact interactions and SO and Rabi couplings (no dipole). Neglecting the repulsive contact interactions, our findings also show the possibility of creating PWSs and SSs. When the strengths of the two interactions are close to each other, the SS develops an oscillatory instability indicating a possibility of a breather solution, eventually leading to its destruction. We also obtain a phase diagram showing regions where the solution is a PWS or SS.

4'-alpha-C-Branched N,O-nucleosides: synthesis and biological properties.

PubMed

Chiacchio, Ugo; Genovese, Filippo; Iannazzo, Daniela; Piperno, Anna; Quadrelli, Paolo; Antonino, Corsaro; Romeo, Roberto; Valveri, Vincenza; Mastino, Antonio

2004-07-15

The synthesis of 4'-alpha-C-branched N,O-nucleosides has been described, based on the 1,3-dipolar cycloaddition of nitrones with vinyl acetate followed by coupling with silylated nucleobases, The obtained compounds have been evaluated for their activity against HSV-1, HSV-2, HTLV-1. Cytotoxicity and apoptotic activity have been also investigated: compound 10c shows moderate apoptotic activity in Molt-3 cells.

Polaron spin echo envelope modulations in an organic semiconducting polymer

DOE PAGES

Mkhitaryan, V. V.; Dobrovitski, V. V.

2017-06-01

Here, we present a theoretical analysis of the electron spin echo envelope modulation (ESEEM) spectra of polarons in semiconducting π -conjugated polymers. We show that the contact hyperfine coupling and the dipolar interaction between the polaron and the proton spins give rise to different features in the ESEEM spectra. Our theory enables direct selective probe of different groups of nuclear spins, which affect the polaron spin dynamics. Namely, we demonstrate how the signal from the distant protons (coupled to the polaron spin via dipolar interactions) can be distinguished from the signal coming from the protons residing on the polaron sitemore » (coupled to the polaron spin via contact hyperfine interaction). We propose a method for directly probing the contact hyperfine interaction, that would enable detailed study of the polaron orbital state and its immediate environment. Lastly, we also analyze the decay of the spin echo modulation, and its connection to the polaron transport.« less

Proton-Based Ultrafast Magic Angle Spinning Solid-State NMR Spectroscopy.

PubMed

Zhang, Rongchun; Mroue, Kamal H; Ramamoorthy, Ayyalusamy

2017-04-18

Protons are vastly abundant in a wide range of exciting macromolecules and thus can be a powerful probe to investigate the structure and dynamics at atomic resolution using solid-state NMR (ssNMR) spectroscopy. Unfortunately, the high signal sensitivity, afforded by the high natural-abundance and high gyromagnetic ratio of protons, is greatly compromised by severe line broadening due to the very strong 1 H- 1 H dipolar couplings. As a result, protons are rarely used, in spite of the desperate need for enhancing the sensitivity of ssNMR to study a variety of systems that are not amenable for high resolution investigation using other techniques including X-ray crystallography, cryo-electron microscopy, and solution NMR spectroscopy. Thanks to the remarkable improvement in proton spectral resolution afforded by the significant advances in magic-angle-spinning (MAS) probe technology, 1 H ssNMR spectroscopy has recently attracted considerable attention in the structural and dynamics studies of various molecular systems. However, it still remains a challenge to obtain narrow 1 H spectral lines, especially from proteins, without resorting to deuteration. In this Account, we review recent proton-based ssNMR strategies that have been developed in our laboratory to further improve proton spectral resolution without resorting to chemical deuteration for the purposes of gaining atomistic-level insights into molecular structures of various crystalline solid systems, using small molecules and peptides as illustrative examples. The proton spectral resolution enhancement afforded by the ultrafast MAS frequencies up to 120 kHz is initially discussed, followed by a description of an ensemble of multidimensional NMR pulse sequences, all based on proton detection, that have been developed to obtain in-depth information from dipolar couplings and chemical shift anisotropy (CSA). Simple single channel multidimensional proton NMR experiments could be performed to probe the proximity of protons for structure determination using 1 H- 1 H dipolar couplings and to evaluate the changes in chemical environments as well as the relative orientation to the external magnetic field using proton CSA. Due to the boost in signal sensitivity enabled by proton detection under ultrafast MAS, by virtue of high proton natural abundance and gyromagnetic ratio, proton-detected multidimensional experiments involving low-γ nuclei can now be accomplished within a reasonable time, while the higher dimension also offers additional resolution enhancement. In addition, the application of proton-based ssNMR spectroscopy under ultrafast MAS in various challenging and crystalline systems is also presented. Finally, we briefly discuss the limitations and challenges pertaining to proton-based ssNMR spectroscopy under ultrafast MAS conditions, such as the presence of high-order dipolar couplings, friction-induced sample heating, and limited sample volume. Although there are still a number of challenges that must be circumvented by further developments in radio frequency pulse sequences, MAS probe technology and approaches to prepare NMR-friendly samples, proton-based ssNMR has already gained much popularity in various research domains, especially in proteins where uniform or site-selective deuteration can be relatively easily achieved. In addition, implementation of the recently developed fast data acquisition approaches would also enable further developments in the design and applications of proton-based ultrafast MAS multidimensional ssNMR techniques.

Renormalization group analysis of dipolar Heisenberg model on square lattice

NASA Astrophysics Data System (ADS)

Keleş, Ahmet; Zhao, Erhai

2018-06-01

We present a detailed functional renormalization group analysis of spin-1/2 dipolar Heisenberg model on square lattice. This model is similar to the well-known J1-J2 model and describes the pseudospin degrees of freedom of polar molecules confined in deep optical lattice with long-range anisotropic dipole-dipole interactions. Previous study of this model based on tensor network ansatz indicates a paramagnetic ground state for certain dipole tilting angles which can be tuned in experiments to control the exchange couplings. The tensor ansatz formulated on a small cluster unit cell is inadequate to describe the spiral order, and therefore the phase diagram at high azimuthal tilting angles remains undetermined. Here, we obtain the full phase diagram of the model from numerical pseudofermion functional renormalization group calculations. We show that an extended quantum paramagnetic phase is realized between the Néel and stripe/spiral phases. In this region, the spin susceptibility flows smoothly down to the lowest numerical renormalization group scales with no sign of divergence or breakdown of the flow, in sharp contrast to the flow towards the long-range-ordered phases. Our results provide further evidence that the dipolar Heisenberg model is a fertile ground for quantum spin liquids.

Dipolar collisions of ultracold 23Na87Rb molecules.

NASA Astrophysics Data System (ADS)

Guo, Mingyang; Ye, Xin; He, Junyu; Quéméner, Goulven; González-Martínez, Maykel; Dulieu, Olivier; Wang, Dajun

2017-04-01

Although ultracold polar molecules have long been proposed as a primary candidate for investigating dipolar many body physics, many of their basic properties, like their collisions in external electric fields, are still largely unknown. In fact, despite the successful production of several new ultracold molecular species in the last two years, so far the only available dipolar collision data is still from JILA's fermionic 40K87Rb experiment in 2010. In this talk, we will describe our investigation on dipolar collisions of ultracold bosonic and chemically stable 23Na87Rb molecules which possess a large permanent electric dipole moment. With a moderate electric field, an effective dipole moment large enough to strongly couple higher partial waves into the collisions can be achieved. We will report the influence of this effect on the molecular collisions observed in our experiment. Our theoretical model for understanding these observations will also be presented. This work is supported by the Hong Kong RGC CUHK404712 and the ANR/RGC Joint Research Scheme ACUHK403/13.

Near-Earth plasma sheet boundary dynamics during substorm dipolarization

NASA Astrophysics Data System (ADS)

Nakamura, Rumi; Nagai, Tsugunobu; Birn, Joachim; Sergeev, Victor A.; Le Contel, Olivier; Varsani, Ali; Baumjohann, Wolfgang; Nakamura, Takuma; Apatenkov, Sergey; Artemyev, Anton; Ergun, Robert E.; Fuselier, Stephen A.; Gershman, Daniel J.; Giles, Barbara J.; Khotyaintsev, Yuri V.; Lindqvist, Per-Arne; Magnes, Werner; Mauk, Barry; Russell, Christopher T.; Singer, Howard J.; Stawarz, Julia; Strangeway, Robert J.; Anderson, Brian; Bromund, Ken R.; Fischer, David; Kepko, Laurence; Le, Guan; Plaschke, Ferdinand; Slavin, James A.; Cohen, Ian; Jaynes, Allison; Turner, Drew L.

2017-09-01

We report on the large-scale evolution of dipolarization in the near-Earth plasma sheet during an intense (AL -1000 nT) substorm on August 10, 2016, when multiple spacecraft at radial distances between 4 and 15 R E were present in the night-side magnetosphere. This global dipolarization consisted of multiple short-timescale (a couple of minutes) B z disturbances detected by spacecraft distributed over 9 MLT, consistent with the large-scale substorm current wedge observed by ground-based magnetometers. The four spacecraft of the Magnetospheric Multiscale were located in the southern hemisphere plasma sheet and observed fast flow disturbances associated with this dipolarization. The high-time-resolution measurements from MMS enable us to detect the rapid motion of the field structures and flow disturbances separately. A distinct pattern of the flow and field disturbance near the plasma boundaries was found. We suggest that a vortex motion created around the localized flows resulted in another field-aligned current system at the off-equatorial side of the BBF-associated R1/R2 systems, as was predicted by the MHD simulation of a localized reconnection jet. The observations by GOES and Geotail, which were located in the opposite hemisphere and local time, support this view. We demonstrate that the processes of both Earthward flow braking and of accumulated magnetic flux evolving tailward also control the dynamics in the boundary region of the near-Earth plasma sheet.[Figure not available: see fulltext.

Logic operations based on magnetic-vortex-state networks.

PubMed

Jung, Hyunsung; Choi, Youn-Seok; Lee, Ki-Suk; Han, Dong-Soo; Yu, Young-Sang; Im, Mi-Young; Fischer, Peter; Kim, Sang-Koog

2012-05-22

Logic operations based on coupled magnetic vortices were experimentally demonstrated. We utilized a simple chain structure consisting of three physically separated but dipolar-coupled vortex-state Permalloy disks as well as two electrodes for application of the logical inputs. We directly monitored the vortex gyrations in the middle disk, as the logical output, by time-resolved full-field soft X-ray microscopy measurements. By manipulating the relative polarization configurations of both end disks, two different logic operations are programmable: the XOR operation for the parallel polarization and the OR operation for the antiparallel polarization. This work paves the way for new-type programmable logic gates based on the coupled vortex-gyration dynamics achievable in vortex-state networks. The advantages are as follows: a low-power input signal by means of resonant vortex excitation, low-energy dissipation during signal transportation by selection of low-damping materials, and a simple patterned-array structure.

Retardation effects on the dispersion and propagation of plasmons in metallic nanoparticle chains

NASA Astrophysics Data System (ADS)

Downing, Charles A.; Mariani, Eros; Weick, Guillaume

2018-01-01

We consider a chain of regularly-spaced spherical metallic nanoparticles, where each particle supports three degenerate localized surface plasmons. Due to the dipolar interaction between the nanoparticles, the localized plasmons couple to form extended collective modes. Using an open quantum system approach in which the collective plasmons are interacting with vacuum electromagnetic modes and which, importantly, readily incorporates retardation via the light-matter coupling, we analytically evaluate the resulting radiative frequency shifts of the plasmonic bandstructure. For subwavelength-sized nanoparticles, our analytical treatment provides an excellent quantitative agreement with the results stemming from laborious numerical calculations based on fully-retarded solutions to Maxwell’s equations. Indeed, the explicit expressions for the plasmonic spectrum which we provide showcase how including retardation gives rise to a logarithmic singularity in the bandstructure of transverse-polarized plasmons. We further study the impact of retardation effects on the propagation of plasmonic excitations along the chain. While for the longitudinal modes, retardation has a negligible effect, we find that the retarded dipolar interaction can significantly modify the plasmon propagation in the case of transverse-polarized modes. Moreover, our results elucidate the analogy between radiative effects in nanoplasmonic systems and the cooperative Lamb shift in atomic physics.

Threshold-Voltage Shifts in Organic Transistors Due to Self-Assembled Monolayers at the Dielectric: Evidence for Electronic Coupling and Dipolar Effects.

PubMed

Aghamohammadi, Mahdieh; Rödel, Reinhold; Zschieschang, Ute; Ocal, Carmen; Boschker, Hans; Weitz, R Thomas; Barrena, Esther; Klauk, Hagen

2015-10-21

The mechanisms behind the threshold-voltage shift in organic transistors due to functionalizing of the gate dielectric with self-assembled monolayers (SAMs) are still under debate. We address the mechanisms by which SAMs determine the threshold voltage, by analyzing whether the threshold voltage depends on the gate-dielectric capacitance. We have investigated transistors based on five oxide thicknesses and two SAMs with rather diverse chemical properties, using the benchmark organic semiconductor dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene. Unlike several previous studies, we have found that the dependence of the threshold voltage on the gate-dielectric capacitance is completely different for the two SAMs. In transistors with an alkyl SAM, the threshold voltage does not depend on the gate-dielectric capacitance and is determined mainly by the dipolar character of the SAM, whereas in transistors with a fluoroalkyl SAM the threshold voltages exhibit a linear dependence on the inverse of the gate-dielectric capacitance. Kelvin probe force microscopy measurements indicate this behavior is attributed to an electronic coupling between the fluoroalkyl SAM and the organic semiconductor.

Effect of phase symmetry on the NMR spectrum of acetonitrile oriented in a uniaxial-biaxial-uniaxial phase

NASA Astrophysics Data System (ADS)

Deepak, H. S. Vinay; Yelamaggad, C. V.; Khetrapal, C. L.; Ramanathan, K. V.

2016-09-01

We report here the measurement of the Csbnd H and the Hsbnd H dipolar couplings of the methyl group of acetonitrile oriented in the biaxial liquid crystal potassium laurate/1-decanol/water system. These parameters show large variations when measured as a function of temperature. The variations follow the symmetry of the phase as the liquid crystal goes through the sequence of uniaxial - biaxial - uniaxial phases and show a close correspondence to the phase changes that occur in the liquid crystalline solvent coinciding with the onset of biaxiality. The Hsbnd Csbnd H bond angle calculated after incorporating vibrational corrections to the dipolar couplings is discussed in terms of contributions in the case of the biaxial liquid crystal arising from vibration-rotation interaction effects.

Floquet-Magnus expansion for general N-coupled spins systems in magic-angle spinning nuclear magnetic resonance spectra

NASA Astrophysics Data System (ADS)

Mananga, Eugene Stephane; Charpentier, Thibault

2015-04-01

In this paper we present a theoretical perturbative approach for describing the NMR spectrum of strongly dipolar-coupled spin systems under fast magic-angle spinning. Our treatment is based on two approaches: the Floquet approach and the Floquet-Magnus expansion. The Floquet approach is well known in the NMR community as a perturbative approach to get analytical approximations. Numerical procedures are based on step-by-step numerical integration of the corresponding differential equations. The Floquet-Magnus expansion is a perturbative approach of the Floquet theory. Furthermore, we address the " γ -encoding" effect using the Floquet-Magnus expansion approach. We show that the average over " γ " angle can be performed for any Hamiltonian with γ symmetry.

Effective Mass Calculations for Two-dimensional Gas of Dipolar Fermions

NASA Astrophysics Data System (ADS)

Seydi, I.; Abedinpour, S. H.; Tanatar, B.

2017-06-01

We consider a two-dimensional system of ultracold dipolar fermions with dipole moments aligned in the perpendicular direction. We use the static structure factor information from Fermi-Hypernetted-Chain calculations to obtain the effective many-body dipole-dipole interaction and calculate the many-body effective mass of the system within the G0W approximation to the self-energy. A large cancellation between different contributions to the self-energy results in a weak dependence of the effective mass on the interaction strength over a large range of coupling constants.

Backbone-only restraints for fast determination of the protein fold: The role of paramagnetism-based restraints. Cytochrome b562 as an example

NASA Astrophysics Data System (ADS)

Banci, Lucia; Bertini, Ivano; Felli, Isabella C.; Sarrou, Josephine

2005-02-01

CH α residual dipolar couplings (Δ rdc's) were measured for the oxidized cytochrome b562 from Escherichia coli as a result of its partial self-orientation in high magnetic fields due to the anisotropy of the overall magnetic susceptibility tensor. Both the low spin iron (III) heme and the four-helix bundle fold contribute to the magnetic anisotropy tensor. CH α Δ rdc's, which span a larger range than the analogous NH values (already available in the literature) sample large space variations at variance with NH Δ rdc's, which are largely isooriented within α helices. The whole structure is now significantly refined with the chemical shift index and CH α Δ rdc's. The latter are particularly useful also in defining the molecular magnetic anisotropy parameters. It is shown here that the backbone folding can be conveniently and accurately determined using backbone restraints only, which include NOEs, hydrogen bonds, residual dipolar couplings, pseudocontact shifts, and chemical shift index. All these restraints are easily and quickly determined from the backbone assignment. The calculated backbone structure is comparable to that obtained by using also side chain restraint. Furthermore, the structure obtained with backbone only restraints is, in its whole, very similar to that obtained with the complete set of restraints. The paramagnetism based restraints are shown to be absolutely relevant, especially for Δ rdc's.

Dipolar response of hydrated proteins

NASA Astrophysics Data System (ADS)

Matyushov, Dmitry V.

2012-02-01

The paper presents an analytical theory and numerical simulations of the dipolar response of hydrated proteins in solution. We calculate the effective dielectric constant representing the average dipole moment induced at the protein by a uniform external field. The dielectric constant shows a remarkable variation among the proteins, changing from 0.5 for ubiquitin to 640 for cytochrome c. The former value implies a negative dipolar susceptibility, that is a dia-electric dipolar response and negative dielectrophoresis. It means that ubiquitin, carrying an average dipole of ≃240 D, is expected to repel from the region of a stronger electric field. This outcome is the result of a negative cross-correlation between the protein and water dipoles, compensating for the positive variance of the intrinsic protein dipole in the overall dipolar susceptibility. In contrast to the neutral ubiquitin, charged proteins studied here show para-electric dipolar response and positive dielectrophoresis. The study suggests that the dipolar response of proteins in solution is strongly affected by the coupling of the protein surface charge to the hydration water. The protein-water dipolar cross-correlations are long-ranged, extending ˜2 nm from the protein surface into the bulk. A similar correlation length of about 1 nm is seen for the electrostatic potential produced by the hydration water inside the protein. The analysis of numerical simulations suggests that the polarization of the protein-water interface is highly heterogeneous and does not follow the standard dielectric results for cavities carved in dielectrics. The polarization of the water shell gains in importance, relative to the intrinsic protein dipole, at high frequencies, above the protein Debye peak. The induced interfacial dipole can be either parallel or antiparallel to the protein dipole, depending on the distribution of the protein surface charge. As a result, the high-frequency absorption of the protein solution can be either higher or lower than the absorption of water. Both scenarios have been experimentally observed in the THz window of radiation.

Dipolar response of hydrated proteins.

PubMed

Matyushov, Dmitry V

2012-02-28

The paper presents an analytical theory and numerical simulations of the dipolar response of hydrated proteins in solution. We calculate the effective dielectric constant representing the average dipole moment induced at the protein by a uniform external field. The dielectric constant shows a remarkable variation among the proteins, changing from 0.5 for ubiquitin to 640 for cytochrome c. The former value implies a negative dipolar susceptibility, that is a dia-electric dipolar response and negative dielectrophoresis. It means that ubiquitin, carrying an average dipole of ≃240 D, is expected to repel from the region of a stronger electric field. This outcome is the result of a negative cross-correlation between the protein and water dipoles, compensating for the positive variance of the intrinsic protein dipole in the overall dipolar susceptibility. In contrast to the neutral ubiquitin, charged proteins studied here show para-electric dipolar response and positive dielectrophoresis. The study suggests that the dipolar response of proteins in solution is strongly affected by the coupling of the protein surface charge to the hydration water. The protein-water dipolar cross-correlations are long-ranged, extending ~2 nm from the protein surface into the bulk. A similar correlation length of about 1 nm is seen for the electrostatic potential produced by the hydration water inside the protein. The analysis of numerical simulations suggests that the polarization of the protein-water interface is highly heterogeneous and does not follow the standard dielectric results for cavities carved in dielectrics. The polarization of the water shell gains in importance, relative to the intrinsic protein dipole, at high frequencies, above the protein Debye peak. The induced interfacial dipole can be either parallel or antiparallel to the protein dipole, depending on the distribution of the protein surface charge. As a result, the high-frequency absorption of the protein solution can be either higher or lower than the absorption of water. Both scenarios have been experimentally observed in the THz window of radiation.

Proton-detected 3D {sup 1}H/{sup 13}C/{sup 1}H correlation experiment for structural analysis in rigid solids under ultrafast-MAS above 60 kHz

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Rongchun; Ramamoorthy, Ayyalusamy, E-mail: ramamoor@umich.edu; Nishiyama, Yusuke

2015-10-28

A proton-detected 3D {sup 1}H/{sup 13}C/{sup 1}H chemical shift correlation experiment is proposed for the assignment of chemical shift resonances, identification of {sup 13}C-{sup 1}H connectivities, and proximities of {sup 13}C-{sup 1}H and {sup 1}H-{sup 1}H nuclei under ultrafast magic-angle-spinning (ultrafast-MAS) conditions. Ultrafast-MAS is used to suppress all anisotropic interactions including {sup 1}H-{sup 1}H dipolar couplings, while the finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used to recouple dipolar couplings among protons and the insensitive nuclei enhanced by polarization transfer technique is used to transfer magnetization between heteronuclear spins. The 3D experiment eliminates signals from non-carbon-bonded protonsmore » and non-proton-bonded carbons to enhance spectral resolution. The 2D (F1/F3) {sup 1}H/{sup 1}H and 2D {sup 13}C/{sup 1}H (F2/F3) chemical shift correlation spectra extracted from the 3D spectrum enable the identification of {sup 1}H-{sup 1}H proximity and {sup 13}C-{sup 1}H connectivity. In addition, the 2D (F1/F2) {sup 1}H/{sup 13}C chemical shift correlation spectrum, incorporated with proton magnetization exchange via the fp-RFDR recoupling of {sup 1}H-{sup 1}H dipolar couplings, enables the measurement of proximities between {sup 13}C and even the remote non-carbon-bonded protons. The 3D experiment also gives three-spin proximities of {sup 1}H-{sup 1}H-{sup 13}C chains. Experimental results obtained from powder samples of L-alanine and L-histidine ⋅ H{sub 2}O ⋅ HCl demonstrate the efficiency of the 3D experiment.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roldan, Omar; Quartin, Miguel; Notari, Alessio, E-mail: oaroldan@if.ufrj.br, E-mail: notari@ffn.ub.es, E-mail: mquartin@if.ufrj.br

The aberration and Doppler coupling effects of the Cosmic Microwave Background (CMB) were recently measured by the Planck satellite. The most straightforward interpretation leads to a direct detection of our peculiar velocity β, consistent with the measurement of the well-known dipole. In this paper we discuss the assumptions behind such interpretation. We show that Doppler-like couplings appear from two effects: our peculiar velocity and a second order large-scale effect due to the dipolar part of the gravitational potential. We find that the two effects are exactly degenerate but only if we assume second-order initial conditions from single-field Inflation. Thus, detectingmore » a discrepancy in the value of β from the dipole and the Doppler couplings implies the presence of a primordial non-Gaussianity. We also show that aberration-like signals likewise arise from two independent effects: our peculiar velocity and lensing due to a first order large-scale dipolar gravitational potential, independently on Gaussianity of the initial conditions. In general such effects are not degenerate and so a discrepancy between the measured β from the dipole and aberration could be accounted for by a dipolar gravitational potential. Only through a fine-tuning of the radial profile of the potential it is possible to have a complete degeneracy with a boost effect. Finally we discuss that we also expect other signatures due to integrated second order terms, which may be further used to disentangle this scenario from a simple boost.« less

Improving the resolution in proton-detected through-space heteronuclear multiple quantum correlation NMR spectroscopy.

PubMed

Shen, Ming; Trébosc, J; Lafon, O; Pourpoint, F; Hu, Bingwen; Chen, Qun; Amoureux, J-P

2014-08-01

Connectivities and proximities between protons and low-gamma nuclei can be probed in solid-state NMR spectroscopy using two-dimensional (2D) proton-detected heteronuclear correlation, through Heteronuclear Multiple Quantum Correlation (HMQC) pulse sequence. The indirect detection via protons dramatically enhances the sensitivity. However, the spectra are often broadened along the indirect F1 dimension by the decay of heteronuclear multiple-quantum coherences under the strong (1)H-(1)H dipolar couplings. This work presents a systematic comparison of the performances of various decoupling schemes during the indirect t1 evolution period of dipolar-mediated HMQC (D-HMQC) experiment. We demonstrate that (1)H-(1)H dipolar decoupling sequences during t1, such as symmetry-based schemes, phase-modulated Lee-Goldburg (PMLG) and Decoupling Using Mind-Boggling Optimization (DUMBO), provide better resolution than continuous wave (1)H irradiation. We also report that high resolution requires the preservation of (1)H isotropic chemical shifts during the decoupling sequences. When observing indirectly broad spectra presenting numerous spinning sidebands, the D-HMQC sequence must be fully rotor-synchronized owing to the rotor-synchronized indirect sampling and dipolar recoupling sequence employed. In this case, we propose a solution to reduce artefact sidebands caused by the modulation of window delays before and after the decoupling application during the t1 period. Moreover, we show that (1)H-(1)H dipolar decoupling sequence using Smooth Amplitude Modulation (SAM) minimizes the t1-noise. The performances of the various decoupling schemes are assessed via numerical simulations and compared to 2D (1)H-{(13)C} D-HMQC experiments on [U-(13)C]-L-histidine⋅HCl⋅H2O at various magnetic fields and Magic Angle spinning (MAS) frequencies. Great resolution and sensitivity enhancements resulting from decoupling during t1 period enable the detection of heteronuclear correlation between aliphatic protons and ammonium (14)N sites in L-histidine⋅HCl⋅H2O. Copyright © 2014 Elsevier Inc. All rights reserved.

Temperature- and pressure-dependent infrared spectroscopy of 1-butyl-3-methylimidazolium trifluoromethanesulfonate: A dipolar coupling theory analysis

NASA Astrophysics Data System (ADS)

Burba, Christopher M.; Chang, Hai-Chou

2018-03-01

Continued growth and development of ionic liquids requires a thorough understanding of how cation and anion molecular structure defines the liquid structure of the materials as well as the various properties that make them technologically useful. Infrared spectroscopy is frequently used to assess molecular-level interactions among the cations and anions of ionic liquids because the intramolecular vibrational modes of the ions are sensitive to the local potential energy environments in which they reside. Thus, different interaction modes among the ions may lead to different spectroscopic signatures in the vibrational spectra. Charge organization present in ionic liquids, such as 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4mim]CF3SO3), is frequently modeled in terms of a quasicrystalline structure. Highly structured quasilattices enable the dynamic coupling of vibrationally-induced dipole moments to produce optical dispersion and transverse optical-longitudinal optical (TO-LO) splitting of vibrational modes of the ionic liquid. According to dipolar coupling theory, the degree of TO-LO splitting is predicted to have a linear dependence on the number density of the ionic liquid. Both temperature and pressure will affect the number density of the ionic liquid and, therefore, the amount of TO-LO splitting for this mode. Therefore, we test these relationships through temperature- and pressure-dependent FT-IR spectroscopic studies of [C4mim]CF3SO3, focusing on the totally symmetric Ssbnd O stretching mode for the anion, νs(SO3). Increased temperature decreases the amount of TO-LO splitting for νs(SO3), whereas elevated pressure is found to increase the amount of band splitting. In both cases, the experimental observations follow the general predictions of dipolar coupling theory, thereby supporting the quasilattice model for this ionic liquid.

HIFI-C: a robust and fast method for determining NMR couplings from adaptive 3D to 2D projections.

PubMed

Cornilescu, Gabriel; Bahrami, Arash; Tonelli, Marco; Markley, John L; Eghbalnia, Hamid R

2007-08-01

We describe a novel method for the robust, rapid, and reliable determination of J couplings in multi-dimensional NMR coupling data, including small couplings from larger proteins. The method, "High-resolution Iterative Frequency Identification of Couplings" (HIFI-C) is an extension of the adaptive and intelligent data collection approach introduced earlier in HIFI-NMR. HIFI-C collects one or more optimally tilted two-dimensional (2D) planes of a 3D experiment, identifies peaks, and determines couplings with high resolution and precision. The HIFI-C approach, demonstrated here for the 3D quantitative J method, offers vital features that advance the goal of rapid and robust collection of NMR coupling data. (1) Tilted plane residual dipolar couplings (RDC) data are collected adaptively in order to offer an intelligent trade off between data collection time and accuracy. (2) Data from independent planes can provide a statistical measure of reliability for each measured coupling. (3) Fast data collection enables measurements in cases where sample stability is a limiting factor (for example in the presence of an orienting medium required for residual dipolar coupling measurements). (4) For samples that are stable, or in experiments involving relatively stronger couplings, robust data collection enables more reliable determinations of couplings in shorter time, particularly for larger biomolecules. As a proof of principle, we have applied the HIFI-C approach to the 3D quantitative J experiment to determine N-C' RDC values for three proteins ranging from 56 to 159 residues (including a homodimer with 111 residues in each subunit). A number of factors influence the robustness and speed of data collection. These factors include the size of the protein, the experimental set up, and the coupling being measured, among others. To exhibit a lower bound on robustness and the potential for time saving, the measurement of dipolar couplings for the N-C' vector represents a realistic "worst case analysis". These couplings are among the smallest currently measured, and their determination in both isotropic and anisotropic media demands the highest measurement precision. The new approach yielded excellent quantitative agreement with values determined independently by the conventional 3D quantitative J NMR method (in cases where sample stability in oriented media permitted these measurements) but with a factor of 2-5 in time savings. The statistical measure of reliability, measuring the quality of each RDC value, offers valuable adjunct information even in cases where modest time savings may be realized.

Monte Carlo simulations of kagome lattices with magnetic dipolar interactions

NASA Astrophysics Data System (ADS)

Plumer, Martin; Holden, Mark; Way, Andrew; Saika-Voivod, Ivan; Southern, Byron

Monte Carlo simulations of classical spins on the two-dimensional kagome lattice with only dipolar interactions are presented. In addition to revealing the sixfold-degenerate ground state, the nature of the finite-temperature phase transition to long-range magnetic order is discussed. Low-temperature states consisting of mixtures of degenerate ground-state configurations separated by domain walls can be explained as a result of competing exchange-like and shape-anisotropy-like terms in the dipolar coupling. Fluctuations between pairs of degenerate spin configurations are found to persist well into the ordered state as the temperature is lowered until locking in to a low-energy state. Results suggest that the system undergoes a continuous phase transition at T ~ 0 . 43 in agreement with previous MC simulations but the nature of the ordering process differs. Preliminary results which extend this analysis to the 3D fcc ABC-stacked kagome systems will be presented.

Relaxation spectra and dipolar correlations for flexible polymers with bulky side groups

DOE Office of Scientific and Technical Information (OSTI.GOV)

Diaz-Calleja, R.; Riande, E.; Roman, J.S.

1992-08-06

This paper discusses how relaxation spectra and dipolar correlations for flexible polymers with bulky side groups (PBPA chains) suggest that intermolecular correlations are not very important in this polymer and that {alpha}, {beta}, and {gamma} absorptions exist. TSDC techniques reveal that the {gamma} peak has a smaller activation energy than the {beta}, and the coupling scheme is used to interpret the complex dielectric and mechanical {alpha} relaxations. The anomalous temperature dependence of the glass-rubber relaxation is discussed in terms of the bulkiness of the side group. 23 refs., 8 figs., 3 tabs.

A High-Resolution 3D Separated-Local-Field Experiment by Means of Magic-Angle Turning

PubMed

Hu; Alderman; Pugmire; Grant

1997-05-01

A 3D separated-local-field (SLF) experiment based on the 2D PHORMAT technique is described. In the 3D experiment, the conventional 2D SLF powder pattern for each chemically inequivalent carbon is separated according to their different isotropic chemical shifts. The dipolar coupling constant of a C-H pair, hence the bond distance, and the relative orientation of the chemical-shift tensor to the C-H vector can all be determined for the protonated carbons with a single measurement. As the sample turns at only about 30 Hz in a MAT experiment, the SLF patterns obtained approach those of a stationary sample, and an accuracy in the measurement similar to that obtained on a stationary sample is expected. The technique is demonstrated on 2,6-dimethoxynaphthalene, where the 13 C-1 H separated-local-field powder patterns for the six chemically inequivalent carbons are clearly identified and measured. The observed dipolar coupling for the methoxy carbon is effectively reduced by the fast rotation of the group about its C3 symmetry axis. The average angle between the C-H bond direction and the C3 rotation axis in the OCH3 group is found to be about 66°.

Structure Calculation and Reconstruction of Discrete-State Dynamics from Residual Dipolar Couplings.

PubMed

Cole, Casey A; Mukhopadhyay, Rishi; Omar, Hanin; Hennig, Mirko; Valafar, Homayoun

2016-04-12

Residual dipolar couplings (RDCs) acquired by nuclear magnetic resonance (NMR) spectroscopy are an indispensable source of information in investigation of molecular structures and dynamics. Here, we present a comprehensive strategy for structure calculation and reconstruction of discrete-state dynamics from RDC data that is based on the singular value decomposition (SVD) method of order tensor estimation. In addition to structure determination, we provide a mechanism of producing an ensemble of conformations for the dynamical regions of a protein from RDC data. The developed methodology has been tested on simulated RDC data with ±1 Hz of error from an 83 residue α protein (PDB ID 1A1Z ) and a 213 residue α/β protein DGCR8 (PDB ID 2YT4 ). In nearly all instances, our method reproduced the structure of the protein including the conformational ensemble to within less than 2 Å. On the basis of our investigations, arc motions with more than 30° of rotation are identified as internal dynamics and are reconstructed with sufficient accuracy. Furthermore, states with relative occupancies above 20% are consistently recognized and reconstructed successfully. Arc motions with a magnitude of 15° or relative occupancy of less than 10% are consistently unrecognizable as dynamical regions within the context of ±1 Hz of error.

Molecular self assembly and chiral recognition of copper octacyanophthalocyanine on Au(111): Interplay of intermolecular and molecule-substrate interactions.

NASA Astrophysics Data System (ADS)

Sk, Rejaul; Dhara, Barun; Miller, Joel; Deshpande, Aparna

Submolecular resolution scanning tunneling microscopy (STM) of copper octacyanophthalocyanine, CuPc(CN)8, at 77 K demonstrates that these achiral molecules form a two dimensional (2D) tetramer-based self-assembly upon evaporation onto an atomically flat Au(111) substrate. They assemble in two different structurally chiral configurations upon adsorption on Au(111). Scanning tunneling spectroscopy (STS),acquired at 77 K, unveils the HOMO and LUMO energy levels of this self-assembly. Voltage dependent STM images show that each molecule in both the structurally chiral configurations individually becomes chiral by breaking the mirror symmetry due to the enhanced intermolecular dipolar coupling interaction at the LUMO energy while the individual molecules remain achiral at the HOMO energy and within the HOMO-LUMO gap. At the LUMO energy, the handedness of the each chiral molecule is decided by the direction of the dipolar coupling interaction in the tetramer unit cell. This preference for LUMO energy indicates that this chirality is purely electronic in nature and it manifests on top of the organizational chirality that is present in the self-assembly independent of the orbital energy. Supported by IISER Pune and DAE-BRNS, India (Project No. 2011/20/37C/17/BRNS).

13C-13C dipolar recoupling under very fast magic angle spinning in solid-state nuclear magnetic resonance: Applications to distance measurements, spectral assignments, and high-throughput secondary-structure determination

NASA Astrophysics Data System (ADS)

Ishii, Yoshitaka

2001-05-01

A technique is presented to recouple homonuclear dipolar couplings between dilute spin pairs such as 13C-13C systems under very fast magic angle spinning (MAS) in solid-state nuclear magnetic resonance (NMR) spectroscopy. The presented technique, finite pulse rf driven recoupling (fpRFDR), restores homonuclear dipolar interactions based on constructive usage of finite pulse-width effects in a phase- and symmetry-cycled π-pulse train in which a rotor-synchronous π pulse is applied every rotation period. The restored effective dipolar interaction has the form of a zero-quantum dipolar Hamiltonian for static solids, whose symmetry in spin space is different from that obtained by conventional rf driven recoupling (RFDR) techniques. It is demonstrated that the efficiency of recoupling by fpRFDR is not strongly dependent on chemical shift differences or resonance offsets in contrast to previous recoupling methods under very fast MAS. To realize distance measurements without effects of spin relaxation, a constant-time version of fpRFDR (CT-fpRFDR) is introduced, in which the effective evolution period is varied by refocusing dipolar evolution with a rotor-synchronized solid echo while the total recoupling period is kept constant. From CT-fpRFDR experiments at a spinning speed of 30.3 kHz in a field of 17.6 T, the 13C-13C distance of [1-13C]Ala-[1-13C]Gly-Gly was determined to be 3.27 Å, which agrees well with the value of 3.20 Å obtained by x-ray diffraction. Also, two-dimensional (2D) 13C/13C chemical-shift correlation NMR spectrum in a field of 9.4 T was obtained with fpRFDR for fibrils of the segmentally 13C- and 15N-labeled Alzheimer's β-Amyloid fragments, Aβ16-22 (residues 16-22 taken from the 40-residue Aβ peptide) in which Leu-17 through Ala-21 are uniformly 13C- and 15N-labeled. Most 13C resonances for the main chain as well as for the side chains are assigned based on 2D 13C/13C chemical-shift correlation patterns specific to amino-acid types. Examination of the obtained 13C chemical shifts revealed the formation of β-strand across the entire molecule of Aβ16-22. Possibility of high throughput determination of global main-chain structures based on 13C shifts obtained from 2D 13C/13C chemical-shift correlation under very fast MAS is also discussed for uniformly/segmentally 13C-labeled protein/peptide samples.

Sine-squared shifted pulses for recoupling interactions in solid-state NMR

NASA Astrophysics Data System (ADS)

Jain, Mukul G.; Rajalakshmi, G.; Equbal, Asif; Mote, Kaustubh R.; Agarwal, Vipin; Madhu, P. K.

2017-06-01

Rotational-Echo DOuble-Resonance (REDOR) is a versatile experiment for measuring internuclear distance between two heteronuclear spins in solid-state NMR. At slow to intermediate magic-angle spinning (MAS) frequencies, the measurement of distances between strongly coupled spins is challenging due to rapid dephasing of magnetisation. This problem can be remedied by employing the pulse-shifted version of REDOR known as Shifted-REDOR (S-REDOR) that scales down the recoupled dipolar coupling. In this study, we propose a new variant of the REDOR sequence where the positions of the π pulses are determined by a sine-squared function. This new variant has scaling properties similar to S-REDOR. We use theory, numerical simulations, and experiments to compare the dipolar recoupling efficiencies and the experimental robustness of the three REDOR schemes. The proposed variant has advantages in terms of radiofrequency field requirements at fast MAS frequencies.

Quantitative determination of the conformational properties of partially folded and intrinsically disordered proteins using NMR dipolar couplings.

PubMed

Jensen, Malene Ringkjøbing; Markwick, Phineus R L; Meier, Sebastian; Griesinger, Christian; Zweckstetter, Markus; Grzesiek, Stephan; Bernadó, Pau; Blackledge, Martin

2009-09-09

Intrinsically disordered proteins (IDPs) inhabit a conformational landscape that is too complex to be described by classical structural biology, posing an entirely new set of questions concerning the molecular understanding of functional biology. The characterization of the conformational properties of IDPs, and the elucidation of the role they play in molecular function, is therefore one of the major challenges remaining for modern structural biology. NMR is the technique of choice for studying this class of proteins, providing information about structure, flexibility, and interactions at atomic resolution even in completely disordered states. In particular, residual dipolar couplings (RDCs) have been shown to be uniquely sensitive and powerful tools for characterizing local and long-range structural behavior in disordered proteins. In this review we describe recent applications of RDCs to quantitatively describe the level of local structure and transient long-range order in IDPs involved in viral replication, neurodegenerative disease, and cancer.

Using the phase shift to asymptotically characterize the dipolar mixed modes in post-main-sequence stars

NASA Astrophysics Data System (ADS)

Jiang, C.; Christensen-Dalsgaard, J.; Cunha, M.

2018-03-01

Mixed modes have been extensively observed in post-main-sequence stars by the Kepler and CoRoT space missions. The mixture of the p and g modes can be measured by the dimensionless coefficient q, the so-called coupling strength factor. In this paper, we discuss the utility of the phase shifts θ from the eigenvalue condition for mixed modes as a tool to characterize dipolar mixed modes from the theoretical as well as the practical point of view. Unlike the coupling strength, whose variation in a given star is very small over the relevant frequency range, the phase shifts vary significantly for different modes. The analysis in terms of θ can also provide a better understanding of the pressure and gravity radial order for a given mixed mode. Observed frequencies of the Kepler red-giant star KIC 3744043 are used to test the method. The results are very promising.

Studies of an Isolated 15N- 15N Spin Pair. Off-Angle Fast-Sample-Spinning NMR and Self-Consistent-Field Calculations for Diazo Systems

NASA Astrophysics Data System (ADS)

Challoner, Robin; Harris, Robin K.; Tossell, John A.

1997-05-01

An off-magic-angle spinning study of the nonassociated molecular solid, doubly15N-labeled 5-methyl-2-diazobenzenesulphonic acid hydrochloride (I) is reported. The validity of the off-magic-angle spinning approach under fast-spinning conditions is verified by average Hamiltonian theory. Ab initio SCF calculations were performed on the simpler molecule, C6H5N2+, to provide the shielding parameters, the dipolar coupling between the two nitrogen nuclei, and the electric field gradient existing at both the α-nitrogen and β-nitrogen sites. The calculated values are in good agreement with the shielding and effective dipolar coupling data elucidated in the present investigation, and with a previous study of the two singly15N-labeled isotopomers in which information concerning the electric field gradient at the α and β sites was deduced.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mahalik, J. P.; Sumpter, Bobby G.; Kumar, Rajeev

In this paper, we use a field theory approach to study the effects of permanent dipoles on interpenetration and free energy changes as a function of distance between two identical planar polymer brushes. Melts (i.e., solvent-free) and solvated brushes made up of polymers grafted on nonadsorbing substrates are studied. In particular, the weak coupling limit of the dipolar interactions is considered, which leads to concentration-dependent pairwise interactions, and the effects of orientational order are neglected. It is predicted that a gradual increase in the dipole moment of the polymer segments can lead to attractive interactions between the brushes at intermediatemore » separation distances. Finally, because classical theory of polymer brushes based on the strong stretching limit (SSL) and the standard self-consistent field theory (SCFT) simulations using the Flory’s χ parameter always predicts repulsive interactions at all separations, our work highlights the importance of dipolar interactions in tailoring and accurately predicting forces between polar polymeric interfaces in contact with each other.« less

Electromagnetically induced transparency in planar metamaterials based on guided mode resonance

NASA Astrophysics Data System (ADS)

Sun, Yaru; Chen, Hang; Li, Xiangjun; Hong, Zhi

2017-06-01

We present and numerically demonstrate a novel, electromagnetically induced transparency (EIT) in planar metamaterials (MMs) based on guided mode resonance (GMR). The unit cell of the MM consists of two metallic ring resonators. The GMR with high quality factor (Q) is achieved by changing the distance between the two rings of the MM. Narrow EIT-like spectral response is realized by coupling between a high Q GMR and a low Q dipolar resonance of the MM. Our work could provide another efficient way towards the realization of EIT with large group index using very simple structures.

Obtaining molecular and structural information from 13C-14N systems with 13C FIREMAT experiments.

PubMed

Strohmeier, Mark; Alderman, D W; Grant, David M

2002-04-01

The effect of dipolar coupling to 14N on 13C FIREMAT (five pi replicated magic angle turning) experiments is investigated. A method is developed for fitting the 13C FIREMAT FID employing the full theory to extract the 13C-14N dipolar and 13C chemical shift tensor information. The analysis requires prior knowledge of the electric field gradient (EFG) tensor at the 14N nucleus. In order to validate the method the analysis is done for the amino acids alpha-glycine, gamma-glycine, l-alanine, l-asparagine, and l-histidine on FIREMAT FIDs recorded at 13C frequencies of 50 and 100 MHz. The dipolar and chemical shift data obtained with this analysis are in very good agreement with the previous single-crystal 13C NMR results and neutron diffraction data on alpha-glycine, l-alanine, and l-asparagine. The values for gamma-glycine and l-histidine obtained with this new method are reported for the first time. The uncertainties in the EFG tensor on the resultant 13C chemical shift and dipolar tensor values are assessed. (c) 2002 Elsevier Science (USA).

A practical strategy for the accurate measurement of residual dipolar couplings in strongly aligned small molecules

NASA Astrophysics Data System (ADS)

Liu, Yizhou; Cohen, Ryan D.; Martin, Gary E.; Williamson, R. Thomas

2018-06-01

Accurate measurement of residual dipolar couplings (RDCs) requires an appropriate degree of alignment in order to optimize data quality. An overly weak alignment yields very small anisotropic data that are susceptible to measurement errors, whereas an overly strong alignment introduces extensive anisotropic effects that severely degrade spectral quality. The ideal alignment amplitude also depends on the specific pulse sequence used for the coupling measurement. In this work, we introduce a practical strategy for the accurate measurement of one-bond 13C-1H RDCs up to a range of ca. -300 to +300 Hz, corresponding to an alignment that is an order of magnitude stronger than typically employed for small molecule structural elucidation. This strong alignment was generated in the mesophase of the commercially available poly-γ-(benzyl-L-glutamate) polymer. The total coupling was measured by the simple and well-studied heteronuclear two-dimensional J-resolved experiment, which performs well in the presence of strong anisotropic effects. In order to unequivocally determine the sign of the total coupling and resolve ambiguities in assigning total couplings in the CH2 group, coupling measurements were conducted at an isotropic condition plus two anisotropic conditions of different alignment amplitudes. Most RDCs could be readily extracted from these measurements whereas more complicated spectral effects resulting from strong homonuclear coupling could be interpreted either theoretically or by simulation. Importantly, measurement of these very large RDCs actually offers significantly improved data quality and utility for the structure determination of small organic molecules.

Transition from capacitive coupling to direct charge transfer in asymmetric terahertz plasmonic assemblies.

PubMed

Ahmadivand, Arash; Sinha, Raju; Gerislioglu, Burak; Karabiyik, Mustafa; Pala, Nezih; Shur, Michael

2016-11-15

We experimentally and numerically analyze the charge transfer THz plasmons using an asymmetric plasmonic assembly of metallic V-shaped blocks. The asymmetric design of the blocks allows for the excitation of classical dipolar and multipolar modes due to the capacitive coupling. Introducing a conductive microdisk between the blocks, we facilitated the excitation of the charge transfer plasmons and studied their characteristics along with the capacitive coupling by varying the size of the disk.

Theoretical study of diaquamalonatozinc(II) single crystal for applications in non-linear optical devices

NASA Astrophysics Data System (ADS)

Chakraborty, Mitesh; Rai, Vineet Kumar

2017-12-01

The aim of the present paper is to employ theoretical methods to investigate the zero field splitting (ZFS) parameter and to investigate the position of the dopant in the host. These theoretical calculations have been compared with the empirical results. The superposition model (SPM) with the microscopic spin-Hamiltonian (MSH) theory and the coefficient of fractional parentage have been employed to investigate the dopant manganese(II) ion substitution in the diaquamalonatozinc(II) (DAMZ) single crystal. The magnetic parameters, viz. g-tensor and D-tensor, has been determined by using the ORCA program package developed by F Neese et al. The unrestricted Kohn-Sham orbitals-based Pederson-Khanna (PK) as the unperturbed wave function is observed to be the most suitable for the computational calculation of spin-orbit tensor (D^{SO}) of the axial ZFS parameter D. The effects of spin-spin dipolar couplings are taken into account. The unrestricted natural orbital (UNO) is used for the calculation of spin-spin dipolar contributions to the ZFS tensor. A comparative study of the quantum mechanical treatment of Pederson-Khanna (PK) with coupled perturbation (CP) is reported in the present study. The unrestricted Kohn-Sham-based natural orbital with Pederson-Khanna-type of perturbation approach validates the experimental results in the evaluation of ZFS parameters. The theoretical results are appropriate with the experimental ones and indicate the interstitial occupancy of Mn^{2+} ion in the host matrix.

Precise single-qubit control of the reflection phase of a photon mediated by a strongly-coupled ancilla–cavity system

NASA Astrophysics Data System (ADS)

Motzoi, F.; Mølmer, K.

2018-05-01

We propose to use the interaction between a single qubit atom and a surrounding ensemble of three level atoms to control the phase of light reflected by an optical cavity. Our scheme employs an ensemble dark resonance that is perturbed by the qubit atom to yield a single-atom single photon gate. We show here that off-resonant excitation towards Rydberg states with strong dipolar interactions offers experimentally-viable regimes of operations with low errors (in the 10‑3 range) as required for fault-tolerant optical-photon, gate-based quantum computation. We also propose and analyze an implementation within microwave circuit-QED, where a strongly-coupled ancilla superconducting qubit can be used in the place of the atomic ensemble to provide high-fidelity coupling to microwave photons.

Explosive electromagnetic radiation by the relaxation of a multimode magnon system.

PubMed

Vasyuchka, V I; Serga, A A; Sandweg, C W; Slobodianiuk, D V; Melkov, G A; Hillebrands, B

2013-11-01

Microwave emission from a parametrically pumped ferrimagnetic film of yttrium iron garnet was studied versus the magnon density evolution, which was detected by Brillouin light scattering spectroscopy. It has been found that the shutdown of external microwave pumping leads to an unexpected effect: The conventional monotonic decrease of the population of parametrically injected magnons is accompanied by an explosive behavior of electromagnetic radiation at the magnon frequency. The developed theory shows that this explosion is caused by a nonlinear energy transfer from parametrically driven short-wavelength dipolar-exchange magnons to a long-wavelength dipolar magnon mode effectively coupled to an electromagnetic wave.

Strong Interlayer Magnon-Magnon Coupling in Magnetic Metal-Insulator Hybrid Nanostructures.

PubMed

Chen, Jilei; Liu, Chuanpu; Liu, Tao; Xiao, Yang; Xia, Ke; Bauer, Gerrit E W; Wu, Mingzhong; Yu, Haiming

2018-05-25

We observe strong interlayer magnon-magnon coupling in an on-chip nanomagnonic device at room temperature. Ferromagnetic nanowire arrays are integrated on a 20-nm-thick yttrium iron garnet (YIG) thin film strip. Large anticrossing gaps up to 1.58 GHz are observed between the ferromagnetic resonance of the nanowires and the in-plane standing spin waves of the YIG film. Control experiments and simulations reveal that both the interlayer exchange coupling and the dynamical dipolar coupling contribute to the observed anticrossings. The coupling strength is tunable by the magnetic configuration, allowing the coherent control of magnonic devices.

Strong Interlayer Magnon-Magnon Coupling in Magnetic Metal-Insulator Hybrid Nanostructures

NASA Astrophysics Data System (ADS)

Chen, Jilei; Liu, Chuanpu; Liu, Tao; Xiao, Yang; Xia, Ke; Bauer, Gerrit E. W.; Wu, Mingzhong; Yu, Haiming

2018-05-01

We observe strong interlayer magnon-magnon coupling in an on-chip nanomagnonic device at room temperature. Ferromagnetic nanowire arrays are integrated on a 20-nm-thick yttrium iron garnet (YIG) thin film strip. Large anticrossing gaps up to 1.58 GHz are observed between the ferromagnetic resonance of the nanowires and the in-plane standing spin waves of the YIG film. Control experiments and simulations reveal that both the interlayer exchange coupling and the dynamical dipolar coupling contribute to the observed anticrossings. The coupling strength is tunable by the magnetic configuration, allowing the coherent control of magnonic devices.

Finite-size corrections in simulation of dipolar fluids

NASA Astrophysics Data System (ADS)

Belloni, Luc; Puibasset, Joël

2017-12-01

Monte Carlo simulations of dipolar fluids are performed at different numbers of particles N = 100-4000. For each size of the cubic cell, the non-spherically symmetric pair distribution function g(r,Ω) is accumulated in terms of projections gmnl(r) onto rotational invariants. The observed N dependence is in very good agreement with the theoretical predictions for the finite-size corrections of different origins: the explicit corrections due to the absence of fluctuations in the number of particles within the canonical simulation and the implicit corrections due to the coupling between the environment around a given particle and that around its images in the neighboring cells. The latter dominates in fluids of strong dipolar coupling characterized by low compressibility and high dielectric constant. The ability to clean with great precision the simulation data from these corrections combined with the use of very powerful anisotropic integral equation techniques means that exact correlation functions both in real and Fourier spaces, Kirkwood-Buff integrals, and bridge functions can be derived from box sizes as small as N ≈ 100, even with existing long-range tails. In the presence of dielectric discontinuity with the external medium surrounding the central box and its replica within the Ewald treatment of the Coulombic interactions, the 1/N dependence of the gmnl(r) is shown to disagree with the, yet well-accepted, prediction of the literature.

Site-resolved multiple-quantum filtered correlations and distance measurements by magic-angle spinning NMR: Theory and applications to spins with weak to vanishing quadrupolar couplings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eliav, U., E-mail: amirgo@tau.ac.il, E-mail: eliav@tau.ac.il; Haimovich, A.; Goldbourt, A., E-mail: amirgo@tau.ac.il, E-mail: eliav@tau.ac.il

2016-01-14

We discuss and analyze four magic-angle spinning solid-state NMR methods that can be used to measure internuclear distances and to obtain correlation spectra between a spin I = 1/2 and a half-integer spin S > 1/2 having a small quadrupolar coupling constant. Three of the methods are based on the heteronuclear multiple-quantum and single-quantum correlation experiments, that is, high rank tensors that involve the half spin and the quadrupolar spin are generated. Here, both zero and single-quantum coherence of the half spins are allowed and various coherence orders of the quadrupolar spin are generated, and filtered, via active recoupling ofmore » the dipolar interaction. As a result of generating coherence orders larger than one, the spectral resolution for the quadrupolar nucleus increases linearly with the coherence order. Since the formation of high rank tensors is independent of the existence of a finite quadrupolar interaction, these experiments are also suitable to materials in which there is high symmetry around the quadrupolar spin. A fourth experiment is based on the initial quadrupolar-driven excitation of symmetric high order coherences (up to p = 2S, where S is the spin number) and subsequently generating by the heteronuclear dipolar interaction higher rank (l + 1 or higher) tensors that involve also the half spins. Due to the nature of this technique, it also provides information on the relative orientations of the quadrupolar and dipolar interaction tensors. For the ideal case in which the pulses are sufficiently strong with respect to other interactions, we derive analytical expressions for all experiments as well as for the transferred echo double resonance experiment involving a quadrupolar spin. We show by comparison of the fitting of simulations and the analytical expressions to experimental data that the analytical expressions are sufficiently accurate to provide experimental {sup 7}Li–{sup 13}C distances in a complex of lithium, glycine, and water. Discussion of the regime for which such an approach is valid is given.« less

Fano-like resonance emerging from magnetic and electric plasmon mode coupling in small arrays of gold particles

DOE PAGES

Bakhti, Saïd; Tishchenko, Alexandre V.; Zambrana-Puyalto, Xavier; ...

2016-09-01

In this work we theoretically and experimentally analyze the resonant behavior of individual 3 × 3 gold particle oligomers illuminated under normal and oblique incidence. While this structure hosts both dipolar and quadrupolar electric and magnetic delocalized modes, only dipolar electric and quadrupolar magnetic modes remain at normal incidence. These modes couple into a strongly asymmetric spectral response typical of a Fano-like resonance. In the basis of the coupled mode theory, an analytical representation of the optical extinction in terms of singular functions is used to identify the hybrid modes emerging from the electric and magnetic mode coupling and tomore » interpret the asymmetric line profiles. Especially, we demonstrate that the characteristic Fano line shape results from the spectral interference of a broad hybrid mode with a sharp one. This structure presents a special feature in which the electric field intensity is confined on different lines of the oligomer depending on the illumination wavelength relative to the Fano dip. This Fano-type resonance is experimentally observed performing extinction cross section measurements on arrays of gold nano-disks. The vanishing of the Fano dip when increasing the incidence angle is also experimentally observed in accordance with numerical simulations.« less

Optical Switching Using Transition from Dipolar to Charge Transfer Plasmon Modes in Ge2Sb2Te5 Bridged Metallodielectric Dimers

PubMed Central

Ahmadivand, Arash; Gerislioglu, Burak; Sinha, Raju; Karabiyik, Mustafa; Pala, Nezih

2017-01-01

Capacitive coupling and direct shuttling of charges in nanoscale plasmonic components across a dielectric spacer and through a conductive junction lead to excitation of significantly different dipolar and charge transfer plasmon (CTP) resonances, respectively. Here, we demonstrate the excitation of dipolar and CTP resonant modes in metallic nanodimers bridged by phase-change material (PCM) sections, material and electrical characteristics of which can be controlled by external stimuli. Ultrafast switching (in the range of a few nanoseconds) between amorphous and crystalline phases of the PCM section (here Ge2Sb2Te5 (GST)) allows for designing a tunable plasmonic switch for optical communication applications with significant modulation depth (up to 88%). Judiciously selecting the geometrical parameters and taking advantage of the electrical properties of the amorphous phase of the GST section we adjusted the extinction peak of the dipolar mode at the telecommunication band (λ~1.55 μm), which is considered as the OFF state. Changing the GST phase to crystalline via optical heating allows for direct transfer of charges through the junction between nanodisks and formation of a distinct CTP peak at longer wavelengths (λ~1.85 μm) far from the telecommunication wavelength, which constitutes the ON state. PMID:28205643

Optical Switching Using Transition from Dipolar to Charge Transfer Plasmon Modes in Ge2Sb2Te5 Bridged Metallodielectric Dimers.

PubMed

Ahmadivand, Arash; Gerislioglu, Burak; Sinha, Raju; Karabiyik, Mustafa; Pala, Nezih

2017-02-16

Capacitive coupling and direct shuttling of charges in nanoscale plasmonic components across a dielectric spacer and through a conductive junction lead to excitation of significantly different dipolar and charge transfer plasmon (CTP) resonances, respectively. Here, we demonstrate the excitation of dipolar and CTP resonant modes in metallic nanodimers bridged by phase-change material (PCM) sections, material and electrical characteristics of which can be controlled by external stimuli. Ultrafast switching (in the range of a few nanoseconds) between amorphous and crystalline phases of the PCM section (here Ge 2 Sb 2 Te 5 (GST)) allows for designing a tunable plasmonic switch for optical communication applications with significant modulation depth (up to 88%). Judiciously selecting the geometrical parameters and taking advantage of the electrical properties of the amorphous phase of the GST section we adjusted the extinction peak of the dipolar mode at the telecommunication band (λ~1.55 μm), which is considered as the OFF state. Changing the GST phase to crystalline via optical heating allows for direct transfer of charges through the junction between nanodisks and formation of a distinct CTP peak at longer wavelengths (λ~1.85 μm) far from the telecommunication wavelength, which constitutes the ON state.

Optical Switching Using Transition from Dipolar to Charge Transfer Plasmon Modes in Ge2Sb2Te5 Bridged Metallodielectric Dimers

NASA Astrophysics Data System (ADS)

Ahmadivand, Arash; Gerislioglu, Burak; Sinha, Raju; Karabiyik, Mustafa; Pala, Nezih

2017-02-01

Capacitive coupling and direct shuttling of charges in nanoscale plasmonic components across a dielectric spacer and through a conductive junction lead to excitation of significantly different dipolar and charge transfer plasmon (CTP) resonances, respectively. Here, we demonstrate the excitation of dipolar and CTP resonant modes in metallic nanodimers bridged by phase-change material (PCM) sections, material and electrical characteristics of which can be controlled by external stimuli. Ultrafast switching (in the range of a few nanoseconds) between amorphous and crystalline phases of the PCM section (here Ge2Sb2Te5 (GST)) allows for designing a tunable plasmonic switch for optical communication applications with significant modulation depth (up to 88%). Judiciously selecting the geometrical parameters and taking advantage of the electrical properties of the amorphous phase of the GST section we adjusted the extinction peak of the dipolar mode at the telecommunication band (λ~1.55 μm), which is considered as the OFF state. Changing the GST phase to crystalline via optical heating allows for direct transfer of charges through the junction between nanodisks and formation of a distinct CTP peak at longer wavelengths (λ~1.85 μm) far from the telecommunication wavelength, which constitutes the ON state.

Nuclear magnetic relaxation by the dipolar EMOR mechanism: Multi-spin systems

NASA Astrophysics Data System (ADS)

Chang, Zhiwei; Halle, Bertil

2017-08-01

In aqueous systems with immobilized macromolecules, including biological tissues, the longitudinal spin relaxation of water protons is primarily induced by exchange-mediated orientational randomization (EMOR) of intra- and intermolecular magnetic dipole-dipole couplings. Starting from the stochastic Liouville equation, we have previously developed a rigorous EMOR relaxation theory for dipole-coupled two-spin and three-spin systems. Here, we extend the stochastic Liouville theory to four-spin systems and use these exact results as a guide for constructing an approximate multi-spin theory, valid for spin systems of arbitrary size. This so-called generalized stochastic Redfield equation (GSRE) theory includes the effects of longitudinal-transverse cross-mode relaxation, which gives rise to an inverted step in the relaxation dispersion profile, and coherent spin mode transfer among solid-like spins, which may be regarded as generalized spin diffusion. The GSRE theory is compared to an existing theory, based on the extended Solomon equations, which does not incorporate these phenomena. Relaxation dispersion profiles are computed from the GSRE theory for systems of up to 16 protons, taken from protein crystal structures. These profiles span the range from the motional narrowing limit, where the coherent mode transfer plays a major role, to the ultra-slow motion limit, where the zero-field rate is closely related to the strong-collision limit of the dipolar relaxation rate. Although a quantitative analysis of experimental data is beyond the scope of this work, it is clear from the magnitude of the predicted relaxation rate and the shape of the relaxation dispersion profile that the dipolar EMOR mechanism is the principal cause of water-1H low-field longitudinal relaxation in aqueous systems of immobilized macromolecules, including soft biological tissues. The relaxation theory developed here therefore provides a basis for molecular-level interpretation of endogenous soft-tissue image contrast obtained by the emerging low-field magnetic resonance imaging techniques.

Accurate characterization of weak macromolecular interactions by titration of NMR residual dipolar couplings: application to the CD2AP SH3-C:ubiquitin complex.

PubMed

Ortega-Roldan, Jose Luis; Jensen, Malene Ringkjøbing; Brutscher, Bernhard; Azuaga, Ana I; Blackledge, Martin; van Nuland, Nico A J

2009-05-01

The description of the interactome represents one of key challenges remaining for structural biology. Physiologically important weak interactions, with dissociation constants above 100 muM, are remarkably common, but remain beyond the reach of most of structural biology. NMR spectroscopy, and in particular, residual dipolar couplings (RDCs) provide crucial conformational constraints on intermolecular orientation in molecular complexes, but the combination of free and bound contributions to the measured RDC seriously complicates their exploitation for weakly interacting partners. We develop a robust approach for the determination of weak complexes based on: (i) differential isotopic labeling of the partner proteins facilitating RDC measurement in both partners; (ii) measurement of RDC changes upon titration into different equilibrium mixtures of partially aligned free and complex forms of the proteins; (iii) novel analytical approaches to determine the effective alignment in all equilibrium mixtures; and (iv) extraction of precise RDCs for bound forms of both partner proteins. The approach is demonstrated for the determination of the three-dimensional structure of the weakly interacting CD2AP SH3-C:Ubiquitin complex (K(d) = 132 +/- 13 muM) and is shown, using cross-validation, to be highly precise. We expect this methodology to extend the remarkable and unique ability of NMR to study weak protein-protein complexes.

Accurate characterization of weak macromolecular interactions by titration of NMR residual dipolar couplings: application to the CD2AP SH3-C:ubiquitin complex

PubMed Central

Ortega-Roldan, Jose Luis; Jensen, Malene Ringkjøbing; Brutscher, Bernhard; Azuaga, Ana I.; Blackledge, Martin; van Nuland, Nico A. J.

2009-01-01

The description of the interactome represents one of key challenges remaining for structural biology. Physiologically important weak interactions, with dissociation constants above 100 μM, are remarkably common, but remain beyond the reach of most of structural biology. NMR spectroscopy, and in particular, residual dipolar couplings (RDCs) provide crucial conformational constraints on intermolecular orientation in molecular complexes, but the combination of free and bound contributions to the measured RDC seriously complicates their exploitation for weakly interacting partners. We develop a robust approach for the determination of weak complexes based on: (i) differential isotopic labeling of the partner proteins facilitating RDC measurement in both partners; (ii) measurement of RDC changes upon titration into different equilibrium mixtures of partially aligned free and complex forms of the proteins; (iii) novel analytical approaches to determine the effective alignment in all equilibrium mixtures; and (iv) extraction of precise RDCs for bound forms of both partner proteins. The approach is demonstrated for the determination of the three-dimensional structure of the weakly interacting CD2AP SH3-C:Ubiquitin complex (Kd = 132 ± 13 μM) and is shown, using cross-validation, to be highly precise. We expect this methodology to extend the remarkable and unique ability of NMR to study weak protein–protein complexes. PMID:19359362

Towards homonuclear J solid-state NMR correlation experiments for half-integer quadrupolar nuclei: experimental and simulated 11B MAS spin-echo dephasing and calculated 2J(BB) coupling constants for lithium diborate.

PubMed

Barrow, Nathan S; Yates, Jonathan R; Feller, Steven A; Holland, Diane; Ashbrook, Sharon E; Hodgkinson, Paul; Brown, Steven P

2011-04-07

Magic-angle spinning (MAS) NMR spin-echo dephasing is systematically investigated for the spin I = 3/2 (11)B nucleus in lithium diborate, Li(2)O·2B(2)O(3). A clear dependence on the quadrupolar frequency (ω(Q)(PAS)/2π = 3C(Q)/[4I(2I- 1)]) is observed: the B3 (larger C(Q)) site dephases more slowly than the B4 site at all investigated MAS frequencies (5 to 20 kHz) at 14.1 T. Increasing the MAS frequency leads to markedly slower dephasing for the B3 site, while there is a much less evident effect for the B4 site. Considering samples at 5, 25, 80 (natural abundance) and 100% (11)B isotopic abundance, dephasing becomes faster for both sites as the (11)B isotopic abundance increases. The experimental behaviour is rationalised using density matrix simulations for two and three dipolar-coupled (11)B nuclei. The experimentally observed slower dephasing for the larger C(Q) (B3) site is reproduced in all simulations and is explained by the reintroduction of the dipolar coupling by the so-called "spontaneous quadrupolar-driven recoupling mechanism" having a different dependence on the MAS frequency for different quadrupolar frequencies. Specifically, isolated spin-pair simulations show that the spontaneous quadrupolar-driven recoupling mechanism is most efficient when the quadrupolar frequency is equal to twice the MAS frequency. While for isolated spin-pair simulations, increasing the MAS frequency leads to faster dephasing, agreement with experiment is observed for three-spin simulations which additionally include the homogeneous nature of the homonuclear dipolar coupling network. First-principles calculations, using the GIPAW approach, of the (2)J(11B-11B) couplings in lithium diborate, metaborate and triborate are presented: a clear trend is revealed whereby the (2)J(11B-11B) couplings increase with increasing B-O-B bond angle and B-B distance. However, the calculated (2)J(11B-11B) couplings are small (0.95, 1.20 and 2.65 Hz in lithium diborate), thus explaining why no zero crossing due to J modulation is observed experimentally, even for the sample at 25% (11)B where significant spin-echo intensity remains out to durations of ∼200 ms.

Propagation of Dipolarization Signatures Observed by the Van Allen Probes in the Inner Magnetosphere

NASA Astrophysics Data System (ADS)

Ohtani, S.; Motoba, T.; Gkioulidou, M.; Takahashi, K.; Kletzing, C.

2017-12-01

Dipolarization, the change of the local magnetic field from a stretched to a more dipolar configuration, is one of the most fundamental processes of magnetospheric physics. It is especially critical for the dynamics of the inner magnetosphere. The associated electric field accelerates ions and electrons and transports them closer to Earth. Such injected ions intensify the ring current, and electrons constitute the seed population of the radiation belt. Those ions and electrons may also excite various waves that play important roles in the enhancement and loss of the radiation belt electrons. Despite such critical consequences, the general characteristics of dipolarization in the inner magnetosphere still remain to be understood. The Van Allen Probes mission, which consists of two probes that orbit through the equatorial region of the inner magnetosphere, provides an ideal opportunity to examine dipolarization signatures in the core of the ring current. In the present study we investigate the spatial expansion of the dipolarization region by examining the correlation and time delay of dipolarization signatures observed by the two probes. Whereas in general it requires three-point measurements to deduce the propagation of a signal on a certain plane, we statically examined the observed time delays and found that dipolarization signatures tend to propagate radially inward as well as away from midnight. In this paper we address the propagation of dipolarization signatures quantitatively and compare with the propagation velocities reported previously based on observations made farther away from Earth. We also discuss how often and under what conditions the dipolarization region expands.

Continuous wave protocol for simultaneous polarization and optical detection of P1-center electron spin resonance

NASA Astrophysics Data System (ADS)

Kamp, E. J.; Carvajal, B.; Samarth, N.

2018-01-01

The ready optical detection and manipulation of bright nitrogen vacancy center spins in diamond plays a key role in contemporary quantum information science and quantum metrology. Other optically dark defects such as substitutional nitrogen atoms (`P1 centers') could also become potentially useful in this context if they could be as easily optically detected and manipulated. We develop a relatively straightforward continuous wave protocol that takes advantage of the dipolar coupling between nitrogen vacancy and P1 centers in type 1b diamond to detect and polarize the dark P1 spins. By combining mutual spin flip transitions with radio frequency driving, we demonstrate the simultaneous optical polarization and detection of the electron spin resonance of the P1 center. This technique should be applicable to detecting and manipulating a broad range of dark spin populations that couple to the nitrogen vacancy center via dipolar fields, allowing for quantum metrology using these spin populations.

Simultaneous gauche and anomeric effects in α-substituted sulfoxides.

PubMed

Freitas, Matheus P

2012-09-07

α-Substituted sulfoxides can experience both gauche and anomeric effects, since these compounds have the geometric requirements and strong electron donor and acceptor orbitals which are essential to make operative the hyperconjugative nature of these effects. Indeed, the title effects were calculated to take place for 1,3-oxathiane 3-oxide in polar solution, where dipolar effects are absent or at least minimized, while only the gauche effect is present in 2-fluorothiane 1-oxide. Since the fluorine atom is a suitable probe for structural analysis using NMR, the (1)J(CF) dependence on the rotation around the F-C-S═O dihedral angle of (fluoromethyl)methyl sulfoxide was evaluated; differently from 1,2-difluoroethane and fluoro(methoxy)methane, this coupling constant is at least not exclusively dependent on dipolar interactions (or on hyperconjugation). Because of the nonmonotonic behavior of the (1)J(CF) rotational profile, this coupling constant does not appear to be of significant diagnostic value for probing the conformations of α-fluoro sulfoxides.

Longitudinal domain wall formation in elongated assemblies of ferromagnetic nanoparticles

PubMed Central

Varón, Miriam; Beleggia, Marco; Jordanovic, Jelena; Schiøtz, Jakob; Kasama, Takeshi; Puntes, Victor F.; Frandsen, Cathrine

2015-01-01

Through evaporation of dense colloids of ferromagnetic ~13 nm ε-Co particles onto carbon substrates, anisotropic magnetic dipolar interactions can support formation of elongated particle structures with aggregate thicknesses of 100–400 nm and lengths of up to some hundred microns. Lorenz microscopy and electron holography reveal collective magnetic ordering in these structures. However, in contrast to continuous ferromagnetic thin films of comparable dimensions, domain walls appear preferentially as longitudinal, i.e., oriented parallel to the long axis of the nanoparticle assemblies. We explain this unusual domain structure as the result of dipolar interactions and shape anisotropy, in the absence of inter-particle exchange coupling. PMID:26416297

Dielectric metamaterials with toroidal dipolar response

DOE PAGES

Basharin, Alexey A.; Kafesaki, Maria; Economou, Eleftherios N.; ...

2015-03-27

Toroidal multipoles are the terms missing in the standard multipole expansion; they are usually overlooked due to their relatively weak coupling to the electromagnetic fields. Here, we propose and theoretically study all-dielectric metamaterials of a special class that represent a simple electromagnetic system supporting toroidal dipolar excitations in the THz part of the spectrum. In addition, we show that resonant transmission and reflection of such metamaterials is dominated by toroidal dipole scattering, the neglect of which would result in a misunderstanding interpretation of the metamaterials’ macroscopic response. Due to the unique field configuration of the toroidal mode, the proposed metamaterialsmore » could serve as a platform for sensing or enhancement of light absorption and optical nonlinearities.« less

Design, Synthesis, and Biological Functionality of a Dendrimer-based Modular Drug Delivery Platform

PubMed Central

Mullen, Douglas G.; McNerny, Daniel Q.; Desai, Ankur; Cheng, Xue-min; DiMaggio, Stassi C.; Kotlyar, Alina; Zhong, Yueyang; Qin, Suyang; Kelly, Christopher V.; Thomas, Thommey P.; Majoros, Istvan; Orr, Bradford G.; Baker, James R.; Banaszak Holl, Mark M.

2011-01-01

A modular dendrimer-based drug delivery platform was designed to improve upon existing limitations in single dendrimer systems. Using this modular strategy, a biologically active platform containing receptor mediated targeting and fluorescence imaging modules was synthesized by coupling a folic acid (FA) conjugated dendrimer with a fluorescein isothiocyanate (FITC) conjugated dendrimer. The two different dendrimer modules were coupled via the 1,3-dipolar cycloaddition reaction (‘click’ chemistry) between an alkyne moiety on the surface of the first dendrimer and an azide moiety on the second dendrimer. Two simplified model systems were also synthesized to develop appropriate ‘click’ reaction conditions and aid in spectroscopic assignments. Conjugates were characterized by 1H NMR spectroscopy and NOESY. The FA-FITC modular platform was evaluated in vitro with a human epithelial cancer cell line (KB) and found to specifically target the over-expressed folic acid receptor. PMID:21425790

Characterizing RNA ensembles from NMR data with kinematic models

PubMed Central

Fonseca, Rasmus; Pachov, Dimitar V.; Bernauer, Julie; van den Bedem, Henry

2014-01-01

Functional mechanisms of biomolecules often manifest themselves precisely in transient conformational substates. Researchers have long sought to structurally characterize dynamic processes in non-coding RNA, combining experimental data with computer algorithms. However, adequate exploration of conformational space for these highly dynamic molecules, starting from static crystal structures, remains challenging. Here, we report a new conformational sampling procedure, KGSrna, which can efficiently probe the native ensemble of RNA molecules in solution. We found that KGSrna ensembles accurately represent the conformational landscapes of 3D RNA encoded by NMR proton chemical shifts. KGSrna resolves motionally averaged NMR data into structural contributions; when coupled with residual dipolar coupling data, a KGSrna ensemble revealed a previously uncharacterized transient excited state of the HIV-1 trans-activation response element stem–loop. Ensemble-based interpretations of averaged data can aid in formulating and testing dynamic, motion-based hypotheses of functional mechanisms in RNAs with broad implications for RNA engineering and therapeutic intervention. PMID:25114056

Molecular dynamic heterogeneity of confined lipid films by 1H magnetization-exchange nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Buda, A.; Demco, D. E.; Jagadeesh, B.; Blümich, B.

2005-01-01

The molecular dynamic heterogeneity of monolayer to submonolayer thin lecithin films confined to submicron cylindrical pores were investigated by 1H magnetization exchange nuclear magnetic resonance. In this experiment a z-magnetization gradient was generated by a double-quantum dipolar filter. The magnetization-exchange decay and buildup curves were interpreted with the help of a theoretical model based on the approximation of a one-dimensional spin-diffusion process in a three-domain morphology. The dynamic heterogeneity of the fatty acid chains and the effects of the surface area per molecule, the diameter of the pores, and the temperature were characterized with the help of local spin-diffusion coefficients. The effect of various parameters on the molecular dynamics of the mobile region of the fatty acid chains was quantified by introducing an ad hoc Gaussian distribution function of the 1H residual dipolar couplings. For the lipid films investigated in this study, the surface induced order and the geometrical confinement affect the chain dynamics of the entire molecule. Therefore, each part of the chain independently reflects the effect of surface coverage, pore size, and temperature.

Equilibrium phases of dipolar lattice bosons in the presence of random diagonal disorder

NASA Astrophysics Data System (ADS)

Zhang, C.; Safavi-Naini, A.; Capogrosso-Sansone, B.

2018-01-01

Ultracold gases offer an unprecedented opportunity to engineer disorder and interactions in a controlled manner. In an effort to understand the interplay between disorder, dipolar interactions, and quantum degeneracy, we study two-dimensional hard-core dipolar lattice bosons in the presence of on-site bound disorder. Our results are based on large-scale path-integral quantum Monte Carlo simulations by the worm algorithm. We study the ground-state phase diagram at a fixed half-integer filling factor for which the clean system is either a superfluid at a lower dipolar interaction strength or a checkerboard solid at a larger dipolar interaction strength. We find that, even for weak dipolar interactions, superfluidity is destroyed in favor of a Bose glass at a relatively low disorder strength. Interestingly, in the presence of disorder, superfluidity persists for values of the dipolar interaction strength for which the clean system is a checkerboard solid. At a fixed disorder strength, as the dipolar interaction is increased, superfluidity is destroyed in favor of a Bose glass. As the interaction is further increased, the system eventually develops extended checkerboard patterns in the density distribution. Due to the presence of disorder, though, grain boundaries and defects, responsible for a finite residual compressibility, are present in the density distribution. Finally, we study the robustness of the superfluid phase against thermal fluctuations.

Metastability in the Spin-1 Blume-Emery-Griffiths Model within Constant Coupling Approximation

NASA Astrophysics Data System (ADS)

Ekiz, C.

2017-02-01

In this paper, the equilibrium properties of spin-1 Blume-Emery-Griffiths model are studied by using constant-coupling approximation. The dipolar and quadrupolar order parameters, the stable, metastable and unstable states and free energy of the model are investigated. The states are defined in terms of local minima of the free energy of system. The numerical calculations are presented for several values of exchange interactions on the simple cubic lattice with q = 6.

Highly Sensitive Refractive Index Sensors with Plasmonic Nanoantennas-Utilization of Optimal Spectral Detuning of Fano Resonances.

PubMed

Mesch, Martin; Weiss, Thomas; Schäferling, Martin; Hentschel, Mario; Hegde, Ravi S; Giessen, Harald

2018-05-25

We analyze and optimize the performance of coupled plasmonic nanoantennas for refractive index sensing. The investigated structure supports a sub- and super-radiant mode that originates from the weak coupling of a dipolar and quadrupolar mode, resulting in a Fano-type spectral line shape. In our study, we vary the near-field coupling of the two modes and particularly examine the influence of the spectral detuning between them on the sensing performance. Surprisingly, the case of matched resonance frequencies does not provide the best sensor. Instead, we find that the right amount of coupling strength and spectral detuning allows for achieving the ideal combination of narrow line width and sufficient excitation strength of the subradiant mode, and therefore results in optimized sensor performance. Our findings are confirmed by experimental results and first-order perturbation theory. The latter is based on the resonant state expansion and provides direct access to resonance frequency shifts and line width changes as well as the excitation strength of the modes. Based on these parameters, we define a figure of merit that can be easily calculated for different sensing geometries and agrees well with the numerical and experimental results.

Efficiency for preforming molecules from mixtures of light Fermi and heavy Bose atoms in optical lattices: The strong-coupling-expansion method

NASA Astrophysics Data System (ADS)

Hu, Anzi; Freericks, J. K.; Maśka, M. M.; Williams, C. J.

2011-04-01

We discuss the application of a strong-coupling expansion (perturbation theory in the hopping) for studying light-Fermi-heavy-Bose (like K40-Rb87) mixtures in optical lattices. We use the strong-coupling method to evaluate the efficiency for preforming molecules, the entropy per particle, and the thermal fluctuations. We show that within the strong interaction regime (and at high temperature), the strong-coupling expansion is an economical way to study this problem. In some cases, it remains valid even down to low temperatures. Because the computational effort is minimal, the strong-coupling approach allows us to work with much larger system sizes, where boundary effects can be eliminated, which is particularly important at higher temperatures. Since the strong-coupling approach is so efficient and accurate, it allows one to rapidly scan through parameter space in order to optimize the preforming of molecules on a lattice (by choosing the lattice depth and interspecies attraction). Based on the strong-coupling calculations, we test the thermometry scheme based on the fluctuation-dissipation theorem and find the scheme gives accurate temperature estimation even at very low temperature. We believe this approach and the calculation results will be useful in the design of the next generation of experiments and will hopefully lead to the ability to form dipolar matter in the quantum degenerate regime.

Structures of invisible, excited protein states by relaxation dispersion NMR spectroscopy

PubMed Central

Vallurupalli, Pramodh; Hansen, D. Flemming; Kay, Lewis E.

2008-01-01

Molecular function is often predicated on excursions between ground states and higher energy conformers that can play important roles in ligand binding, molecular recognition, enzyme catalysis, and protein folding. The tools of structural biology enable a detailed characterization of ground state structure and dynamics; however, studies of excited state conformations are more difficult because they are of low population and may exist only transiently. Here we describe an approach based on relaxation dispersion NMR spectroscopy in which structures of invisible, excited states are obtained from chemical shifts and residual anisotropic magnetic interactions. To establish the utility of the approach, we studied an exchanging protein (Abp1p SH3 domain)–ligand (Ark1p peptide) system, in which the peptide is added in only small amounts so that the ligand-bound form is invisible. From a collection of 15N, 1HN, 13Cα, and 13CO chemical shifts, along with 1HN-15N, 1Hα-13Cα, and 1HN-13CO residual dipolar couplings and 13CO residual chemical shift anisotropies, all pertaining to the invisible, bound conformer, the structure of the bound state is determined. The structure so obtained is cross-validated by comparison with 1HN-15N residual dipolar couplings recorded in a second alignment medium. The methodology described opens up the possibility for detailed structural studies of invisible protein conformers at a level of detail that has heretofore been restricted to applications involving visible ground states of proteins. PMID:18701719

Interparticle coupling effect of silver-gold heterodimer to enhance light harvesting in ultrathin perovskite solar cell

NASA Astrophysics Data System (ADS)

Hu, Zhaosheng; Ma, Tingli; Hayase, Shuzi

2018-01-01

Thin perovskite solar cells are under intensive interest since they reduce the amount of absorber layer, especially toxic lead in methylammonium lead iodide (MAPbI3) devices and have wide application in semitransparent and tandem solar cells. However, due to the decrease of the layer thickness, thin perovskite devices with weak light-harvesting have poor performance. Moreover, the performance of plasmonic thin perovskite devices by incorporating noncoupling metal NPs cannot give comparable performance with normal devices. In this perspective, we discuss the implication of employing random silver-gold heterodimers in MAPbI3 solar cells with the aim of establishing some guidelines for the efficient ultrathin perovskite solar cells. This method induces an extraordinarily high light-harvesting for ultrathin perovskite film. And the underlying physical mechanism behind the enhanced absorption is deeply investigated by plasmon hybridization, dipolar-dipolar coupling method and FDTD simulation. We notice that perovskite embedded silver-gold heterodimer overcomes the vanished antibonding plasmon resononse (σ * ) in nonjunction area of gold/silver homodimer. A 150-nm perovskite film with embedded random silver-gold heterodimers with 80 nm size and 25 nm gap distance processes 28.15% absorption enhancement compared to the reference film, which is higher than the reported 10% for gold homodimers. And we also predict a realistic solution-processed, easy, and low-cost fabrication method, which provide a means to realize highly efficient ultrathin perovskite solar cell including other absorber-based photovoltaics.

Quantum factorization of 143 on a dipolar-coupling nuclear magnetic resonance system.

PubMed

Xu, Nanyang; Zhu, Jing; Lu, Dawei; Zhou, Xianyi; Peng, Xinhua; Du, Jiangfeng

2012-03-30

Quantum algorithms could be much faster than classical ones in solving the factoring problem. Adiabatic quantum computation for this is an alternative approach other than Shor's algorithm. Here we report an improved adiabatic factoring algorithm and its experimental realization to factor the number 143 on a liquid-crystal NMR quantum processor with dipole-dipole couplings. We believe this to be the largest number factored in quantum-computation realizations, which shows the practical importance of adiabatic quantum algorithms.

Simultaneous use of solution NMR and X-ray data in REFMAC5 for joint refinement/detection of structural differences.

PubMed

Rinaldelli, Mauro; Ravera, Enrico; Calderone, Vito; Parigi, Giacomo; Murshudov, Garib N; Luchinat, Claudio

2014-04-01

The program REFMAC5 from CCP4 was modified to allow the simultaneous use of X-ray crystallographic data and paramagnetic NMR data (pseudocontact shifts and self-orientation residual dipolar couplings) and/or diamagnetic residual dipolar couplings. Incorporation of these long-range NMR restraints in REFMAC5 can reveal differences between solid-state and solution conformations of molecules or, in their absence, can be used together with X-ray crystallographic data for structural refinement. Since NMR and X-ray data are complementary, when a single structure is consistent with both sets of data and still maintains reasonably `ideal' geometries, the reliability of the derived atomic model is expected to increase. The program was tested on five different proteins: the catalytic domain of matrix metalloproteinase 1, GB3, ubiquitin, free calmodulin and calmodulin complexed with a peptide. In some cases the joint refinement produced a single model consistent with both sets of observations, while in other cases it indicated, outside the experimental uncertainty, the presence of different protein conformations in solution and in the solid state.

Understanding the Origins of Dipolar Couplings and Correlated Motion in the Vibrational Spectrum of Water.

PubMed

Heyden, Matthias; Sun, Jian; Forbert, Harald; Mathias, Gerald; Havenith, Martina; Marx, Dominik

2012-08-16

The combination of vibrational spectroscopy and molecular dynamics simulations provides a powerful tool to obtain insights into the molecular details of water structure and dynamics in the bulk and in aqueous solutions. Applying newly developed approaches to analyze correlations of charge currents, molecular dipole fluctuations, and vibrational motion in real and k-space, we compare results from nonpolarizable water models, widely used in biomolecular modeling, to ab initio molecular dynamics. For the first time, we unfold the infrared response of bulk water into contributions from correlated fluctuations in the three-dimensional, anisotropic environment of an average water molecule, from the OH-stretching region down to the THz regime. Our findings show that the absence of electronic polarizability in the force field model not only results in differences in dipolar couplings and infrared absorption but also induces artifacts into the correlated vibrational motion between hydrogen-bonded water molecules, specifically at the intramolecular bending frequency. Consequently, vibrational motion is partially ill-described with implications for the accuracy of non-self-consistent, a posteriori methods to add polarizability.

High-Temperature and High-Energy-Density Dipolar Glass Polymers Based on Sulfonylated Poly(2,6-dimethyl-1,4-phenylene oxide).

PubMed

Zhang, Zhongbo; Wang, David H; Litt, Morton H; Tan, Loon-Seng; Zhu, Lei

2018-02-05

A new class of high-temperature dipolar polymers based on sulfonylated poly(2,6-dimethyl-1,4-phenylene oxide) (SO 2 -PPO) was synthesized by post-polymer functionalization. Owing to the efficient rotation of highly polar methylsulfonyl side groups below the glass transition temperature (T g ≈220 °C), the dipolar polarization of these SO 2 -PPOs was enhanced, and thus the dielectric constant was high. Consequently, the discharge energy density reached up to 22 J cm -3 . Owing to its high T g  , the SO 2 -PPO 25 sample also exhibited a low dielectric loss. For example, the dissipation factor (tan δ) was 0.003, and the discharge efficiency at 800 MV m -1 was 92 %. Therefore, these dipolar glass polymers are promising for high-temperature, high-energy-density, and low-loss electrical energy storage applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluating the Performance of the ff99SB Force Field Based on NMR Scalar Coupling Data

PubMed Central

Wickstrom, Lauren; Okur, Asim; Simmerling, Carlos

2009-01-01

Abstract Force-field validation is essential for the identification of weaknesses in current models and the development of more accurate models of biomolecules. NMR coupling and relaxation methods have been used to effectively diagnose the strengths and weaknesses of many existing force fields. Studies using the ff99SB force field have shown excellent agreement between experimental and calculated order parameters and residual dipolar calculations. However, recent studies have suggested that ff99SB demonstrates poor agreement with J-coupling constants for short polyalanines. We performed extensive replica-exchange molecular-dynamics simulations on Ala3 and Ala5 in TIP3P and TIP4P-Ew solvent models. Our results suggest that the performance of ff99SB is among the best of currently available models. In addition, scalar coupling constants derived from simulations in the TIP4P-Ew model show a slight improvement over those obtained using the TIP3P model. Despite the overall excellent agreement, the data suggest areas for possible improvement. PMID:19651043

Decoherence mechanisms in Mn3 single-molecule magnet

NASA Astrophysics Data System (ADS)

Abeywardana, C.; Mowson, A. M.; Christou, G.; Takahashi, S.

In spite of wide interest in the quantum nature of SMMs, decoherence effects that ultimately limit such behavior have yet to be fully understood. Recent investigations have shown that there are three main decoherence mechanisms present in SMMs: spins can couple locally (i) to phonons (phonon decoherence); (ii) to many nuclear spins (nuclear decoherence); and (iii) to each other via dipolar interactions (dipolar decoherence). We have recently uncovered quantum coherence in a Mn3 SMM by quenching decoherence due to dipole interaction between SMMs using a high frequency electron paramagnetic resonance and low temperature. In this presentation, we will discuss temperature dependence of spin relaxation times and the decoherence mechanisms in the Mn3 SMM. This work is supported by the National Science Foundation (DMR-1508661) and the Searle scholars program.

Deuterium REDOR: Principles and Applications for Distance Measurements

NASA Astrophysics Data System (ADS)

Sack, I.; Goldbourt, A.; Vega, S.; Buntkowsky, G.

1999-05-01

The application of short composite pulse schemes ([figure] and [figure]) to the rotational echo double-resonance (REDOR) spectroscopy ofX-2H (X: spin{1}/{2}, observed) systems with large deuterium quadrupolar interactions has been studied experimentally and theoretically and compared with simple 180° pulse schemes. The basic properties of the composite pulses on the deuterium nuclei have been elucidated, using average Hamiltonian theory, and exact simulations of the experiments have been achieved by stepwise integration of the equation of motion of the density matrix. REDOR experiments were performed on15N-2H in doubly labeled acetanilide and on13C-2H in singly2H-labeled acetanilide. The most efficient REDOR dephasing was observed when [figure] composite pulses were used. It is found that the dephasing due to simple 180° deuterium pulses is about a factor of 2 less efficient than the dephasing due to the composite pulse sequences and thus the range of couplings observable byX-2H REDOR is enlarged toward weaker couplings, i.e., larger distances. From these experiments the2H-15N dipolar coupling between the amino deuteron and the amino nitrogen and the2H-13C dipolar couplings between the amino deuteron and the α and β carbons have been elucidated and the corresponding distances have been determined. The distance data from REDOR are in good agreement with data from X-ray and neutron diffraction, showing the power of the method.

Transfer of dipolar gas through the discrete localized mode.

PubMed

Bai, Xiao-Dong; Zhang, Ai-Xia; Xue, Ju-Kui

2013-12-01

By considering the discrete nonlinear Schrödinger model with dipole-dipole interactions for dipolar condensate, the existence, the types, the stability, and the dynamics of the localized modes in a nonlinear lattice are discussed. It is found that the contact interaction and the dipole-dipole interactions play important roles in determining the existence, the type, and the stability of the localized modes. Because of the coupled effects of the contact interaction and the dipole-dipole interactions, rich localized modes and their stability nature can exist: when the contact interaction is larger and the dipole-dipole interactions is smaller, a discrete bright breather occurs. In this case, while the on-site interaction can stabilize the discrete breather, the dipole-dipole interactions will destabilize the discrete breather; when both the contact interaction and the dipole-dipole interactions are larger, a discrete kink appears. In this case, both the on-site interaction and the dipole-dipole interactions can stabilize the discrete kink, but the discrete kink is more unstable than the ordinary discrete breather. The predicted results provide a deep insight into the dynamics of blocking, filtering, and transfer of the norm in nonlinear lattices for dipolar condensates.

Tuning the Origin of Magnetic Relaxation by Substituting the 3d or Rare-Earth Ions into Three Isostructural Cyano-Bridged 3d-4f Heterodinuclear Compounds.

PubMed

Zhang, Yan; Guo, Zhen; Xie, Shuang; Li, Hui-Li; Zhu, Wen-Hua; Liu, Li; Dong, Xun-Qing; He, Wei-Xun; Ren, Jin-Chao; Liu, Ling-Zhi; Powell, Annie K

2015-11-02

Three isostructural cyano-bridged 3d-4f compounds, [YFe(CN)6(hep)2(H2O)4] (1), [DyFe(CN)6(hep)2(H2O)4] (2), and [DyCo(CN)6(hep)2(H2O)4] (3), were successfully assembled by site-targeted substitution of the 3d or rare-earth ions. All compounds have been structurally characterized to display slightly distorted pentagonal-bipyramidal local coordination geometry around the rare-earth ions. Magnetic analyses revealed negligible magnetic coupling in compound 1, antiferromagnetic intradimer interaction in 2, and weak ferromagnetic coupling through dipolar-dipolar interaction in 3. Under an applied direct-current (dc) field, 1 (Hdc = 2.5 kOe, τ0 = 1.3 × 10(-7) s, and Ueff/kB = 23 K) and 3 (Hdc = 2.0 kOe, τ0 = 7.1 × 10(-11) s, and Ueff/kB = 63 K) respectively indicated magnetic relaxation behavior based on a single [Fe(III)]LS ion and a Dy(III) ion; nevertheless, 2 (Hdc = 2.0 kOe, τ0 = 9.7 × 10(-8) s, and Ueff/kB = 23 K) appeared to be a single-molecule magnet based on a cyano-bridged DyFe dimer. Compound 1, which can be regarded as a single-ion magnet of the [Fe(III)]LS ion linked to a diamagnetic Y(III) ion in a cyano-bridged heterodimer, represents one of the rarely investigated examples based on a single Fe(III) ion explored in magnetic relaxation behavior. It demonstrated that the introduction of intradimer magnetic interaction of 2 through a cyano bridge between Dy(III) and [Fe(III)]LS ions negatively affects the energy barrier and χ″(T) peak temperature compared to 3.

Experimental realization of a subwavelength optical potential based on atomic dark state

NASA Astrophysics Data System (ADS)

Wang, Yang; Subhankar, Sarthak; Rolston, Steven; Porto, James

2017-04-01

As a well-established tool optical lattice (OL) provides the unique opportunity to exploit the rich manybody physics. However, ``traditional'' OL, either via laser beam interference or direct projection with spatial light modulator, has a length scale around the wavelength (0.1 10 λ) that is set by diffraction, a fundamental limit from the wave nature of the light. Recent theoretical proposals suggest an alternative route, where the geometric potential, stemming from light-atom interaction, can be engineered to generate a much finer potential landscape which is essentially limited by the wave nature of the slow moving cold atoms. We report on the progress towards an experimental realization of these ideas using degenerate fermionic ytterbium atoms. Such subwavelength optical potential could open the gate to study physics beyond currently available parameter regimes, such as enhanced super-exchange coupling, magnetic dipolar coupling, and tunnel junction in atomtronics.

The structure of poly(carbonsuboxide) on the atomic scale: a solid-state NMR study.

PubMed

Schmedt auf der Günne, Jörn; Beck, Johannes; Hoffbauer, Wilfried; Krieger-Beck, Petra

2005-07-18

In this contribution we present a study of the structure of amorphous poly(carbonsuboxide) (C3O2)x by 13C solid-state NMR spectroscopy supported by infrared spectroscopy and chemical analysis. Poly(carbonsuboxide) was obtained by polymerization of carbonsuboxide C3O2, which in turn was synthesized from malonic acid bis(trimethylsilylester). Two different 13C labeling schemes were applied to probe inter- and intramonomeric bonds in the polymer by dipolar solid-state NMR methods and also to allow quantitative 13C MAS NMR spectra. Four types of carbon environments can be distinguished in the NMR spectra. Double-quantum and triple-quantum 2D correlation experiments were used to assign the observed peaks using the through-space and through-bond dipolar coupling. In order to obtain distance constraints for the intermonomeric bonds, double-quantum constant-time experiments were performed. In these experiments an additional filter step was applied to suppress contributions from not directly bonded 13C,13C spin pairs. The 13C NMR intensities, chemical shifts, connectivities and distances gave constraints for both the polymerization mechanism and the short-range order of the polymer. The experimental results were complemented by bond lengths predicted by density functional theory methods for several previously suggested models. Based on the presented evidence we can unambiguously exclude models based on gamma-pyronic units and support models based on alpha-pyronic units. The possibility of planar ladder- and bracelet-like alpha-pyronic structures is discussed.

Hyperfine field and magnetic structure in the B phase of CeCoIn5

DOE Office of Scientific and Technical Information (OSTI.GOV)

Graf, Matthias J; Curro, Nicholas J; Young, Ben - Li

2009-01-01

We re-analyze Nuclear Magnetic Resonance (NMR) spectra observed at low temperatures and high magnetic fields in the field-induced B-phase of CeCoIn{sub 5}. The NMR spectra are consistent with incommensurate antiferromagnetic order of the Ce magnetic moments. However, we find that the spectra of the In(2) sites depend critically on the direction of the ordered moments, the ordering wavevector and the symmetry of the hyperfine coupling to the Ce spins. Assuming isotropic hyperfine coupling, the NMR spectra observed for H {parallel} [100] are consistent with magnetic order with wavevector Q = {pi}(1+{delta}/a, 1/a, 1/c) and Ce moments ordered antiferromagnetically along themore » [100] direction in real space. If the hyperfine coupling has dipolar symmetry, then the NMR spectra require Ce moments along the [001] direction. The dipolar scenario is also consistent with recent neutron scattering measurements that find an ordered moment of 0.15{micro}{sub B} along [001] and Q{sub n} = {pi}(1+{delta}/a, 1+{delta}c, 1/c) with incommensuration {delta} = 0.12 for field H {parallel} [1{bar 1}0]. Using these parameters, we find that the hyperfine field is consistent with both experiments. We speculate that the B phase of CeCoIn{sub 5} represents an intrinsic phase of modulated superconductivity and antiferromagnetism that can only emerge in a highly clean system.« less

Dipolar dark matter with massive bigravity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blanchet, Luc; Heisenberg, Lavinia; Department of Physics & The Oskar Klein Centre, AlbaNova University Centre,Roslagstullsbacken 21, 10691 Stockholm

2015-12-14

Massive gravity theories have been developed as viable IR modifications of gravity motivated by dark energy and the problem of the cosmological constant. On the other hand, modified gravity and modified dark matter theories were developed with the aim of solving the problems of standard cold dark matter at galactic scales. Here we propose to adapt the framework of ghost-free massive bigravity theories to reformulate the problem of dark matter at galactic scales. We investigate a promising alternative to dark matter called dipolar dark matter (DDM) in which two different species of dark matter are separately coupled to the twomore » metrics of bigravity and are linked together by an internal vector field. We show that this model successfully reproduces the phenomenology of dark matter at galactic scales (i.e. MOND) as a result of a mechanism of gravitational polarisation. The model is safe in the gravitational sector, but because of the particular couplings of the matter fields and vector field to the metrics, a ghost in the decoupling limit is present in the dark matter sector. However, it might be possible to push the mass of the ghost beyond the strong coupling scale by an appropriate choice of the parameters of the model. Crucial questions to address in future work are the exact mass of the ghost, and the cosmological implications of the model.« less

Dipolar dark matter with massive bigravity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blanchet, Luc; Heisenberg, Lavinia, E-mail: blanchet@iap.fr, E-mail: laviniah@kth.se

2015-12-01

Massive gravity theories have been developed as viable IR modifications of gravity motivated by dark energy and the problem of the cosmological constant. On the other hand, modified gravity and modified dark matter theories were developed with the aim of solving the problems of standard cold dark matter at galactic scales. Here we propose to adapt the framework of ghost-free massive bigravity theories to reformulate the problem of dark matter at galactic scales. We investigate a promising alternative to dark matter called dipolar dark matter (DDM) in which two different species of dark matter are separately coupled to the twomore » metrics of bigravity and are linked together by an internal vector field. We show that this model successfully reproduces the phenomenology of dark matter at galactic scales (i.e. MOND) as a result of a mechanism of gravitational polarisation. The model is safe in the gravitational sector, but because of the particular couplings of the matter fields and vector field to the metrics, a ghost in the decoupling limit is present in the dark matter sector. However, it might be possible to push the mass of the ghost beyond the strong coupling scale by an appropriate choice of the parameters of the model. Crucial questions to address in future work are the exact mass of the ghost, and the cosmological implications of the model.« less

Spin wave eigenmodes in single and coupled sub-150 nm rectangular permalloy dots

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carlotti, G., E-mail: giovanni.carlotti@fisica.unipg.it; Madami, M.; Tacchi, S.

2015-05-07

We present the results of a Brillouin light scattering investigation of thermally excited spin wave eigenmodes in square arrays of either isolated rectangular dots of permalloy or twins of dipolarly coupled elements, placed side-by-side or head-to-tail. The nanodots, fabricated by e-beam lithography and lift-off, are 20 nm thick and have the major size D in the range between 90 nm and 150 nm. The experimental spectra show the presence of two main peaks, corresponding to modes localized either at the edges or in the center of the dots. Their frequency dependence on the dot size and on the interaction with adjacent elements hasmore » been measured and successfully interpreted on the basis of dynamical micromagnetic simulations. The latter enabled us also to describe the spatial profile of the eigenmodes, putting in evidence the effects induced by the dipolar interaction between coupled dots. In particular, in twinned dots the demagnetizing field is appreciably modified in proximity of the “internal edges” if compared to the “external” ones, leading to a splitting of the edge mode. These results can be relevant for the exploitation of sub-150 nm magnetic dots in new applications, such as magnonic metamaterials, bit-patterned storage media, and nano-magnetic logic devices.« less

Structure of calmodulin complexed with an olfactory CNG channel fragment and role of the central linker: residual dipolar couplings to evaluate calmodulin binding modes outside the kinase family.

PubMed

Contessa, Gian Marco; Orsale, Maria; Melino, Sonia; Torre, Vincent; Paci, Maurizio; Desideri, Alessandro; Cicero, Daniel O

2005-03-01

The NMR high-resolution structure of calmodulin complexed with a fragment of the olfactory cyclic-nucleotide gated channel is described. This structure shows features that are unique for this complex, including an active role of the linker connecting the N- and C-lobes of calmodulin upon binding of the peptide. Such linker is not only involved in the formation of an hydrophobic pocket to accommodate a bulky peptide residue, but it also provides a positively charged region complementary to a negative charge of the target. This complex of calmodulin with a target not belonging to the kinase family was used to test the residual dipolar coupling (RDC) approach for the determination of calmodulin binding modes to peptides. Although the complex here characterized belongs to the (1--14) family, high Q values were obtained with all the 1:1 complexes for which crystalline structures are available. Reduction of the RDC data set used for the correlation analysis to structured regions of the complex allowed a clear identification of the binding mode. Excluded regions comprise calcium binding loops and loops connecting the EF-hand motifs.

Resolution enhancement using a new multiple-pulse decoupling sequence for quadrupolar nuclei.

PubMed

Delevoye, L; Trébosc, J; Gan, Z; Montagne, L; Amoureux, J-P

2007-05-01

A new decoupling composite pulse sequence is proposed to remove the broadening on spin S=1/2 magic-angle spinning (MAS) spectra arising from the scalar coupling with a quadrupolar nucleus I. It is illustrated on the (31)P spectrum of an aluminophosphate, AlPO(4)-14, which is broadened by the presence of (27)Al/(31)P scalar couplings. The multiple-pulse (MP) sequence has the advantage over the continuous wave (CW) irradiation to efficiently annul the scalar dephasing without reintroducing the dipolar interaction. The MP decoupling sequence is first described in a rotor-synchronised version (RS-MP) where one parameter only needs to be adjusted. It clearly avoids the dipolar recoupling in order to achieve a better resolution than using the CW sequence. In a second improved version, the MP sequence is experimentally studied in the vicinity of the perfect rotor-synchronised conditions. The linewidth at half maximum (FWHM) of 65 Hz using (27)Al CW decoupling decreases to 48 Hz with RS-MP decoupling and to 30 Hz with rotor-asynchronised MP (RA-MP) decoupling. The main phenomena are explained using both experimental results and numerical simulations.

Dielectric relaxation in ionic liquid/dipolar solvent binary mixtures: A semi-molecular theory.

PubMed

Daschakraborty, Snehasis; Biswas, Ranjit

2016-03-14

A semi-molecular theory is developed here for studying dielectric relaxation (DR) in binary mixtures of ionic liquids (ILs) with common dipolar solvents. Effects of ion translation on DR time scale, and those of ion rotation on conductivity relaxation time scale are explored. Two different models for the theoretical calculations have been considered: (i) separate medium approach, where molecularities of both the IL and dipolar solvent molecules are retained, and (ii) effective medium approach, where the added dipolar solvent molecules are assumed to combine with the dipolar ions of the IL, producing a fictitious effective medium characterized via effective dipole moment, density, and diameter. Semi-molecular expressions for the diffusive DR times have been derived which incorporates the effects of wavenumber dependent orientational static correlations, ion dynamic structure factors, and ion translation. Subsequently, the theory has been applied to the binary mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]) with water (H2O), and acetonitrile (CH3CN) for which experimental DR data are available. On comparison, predicted DR time scales show close agreement with the measured DR times at low IL mole fractions (x(IL)). At higher IL concentrations (x(IL) > 0.05), the theory over-estimates the relaxation times and increasingly deviates from the measurements with x(IL), deviation being the maximum for the neat IL by almost two orders of magnitude. The theory predicts negligible contributions to this deviation from the x(IL) dependent collective orientational static correlations. The drastic difference between DR time scales for IL/solvent mixtures from theory and experiments arises primarily due to the use of the actual molecular volume (V(mol)(dip)) for the rotating dipolar moiety in the present theory and suggests that only a fraction of V(mol)(dip) is involved at high x(IL). Expectedly, nice agreement between theory and experiments appears when experimental estimates for the effective rotational volume (V(eff)(dip)) are used as inputs. The fraction, V(eff)(dip)/V(mol)(dip), sharply decreases from ∼1 at pure dipolar solvent to ∼0.01 at neat IL, reflecting a dramatic crossover from viscosity-coupled hydrodynamic angular diffusion at low IL mole fractions to orientational relaxation predominantly via large angle jumps at high x(IL). Similar results are obtained on applying the present theory to the aqueous solution of an electrolyte guanidinium chloride (GdmCl) having a permanent dipole moment associated with the cation, Gdm(+).

An introduction to NMR-based approaches for measuring protein dynamics

PubMed Central

Kleckner, Ian R; Foster, Mark P

2010-01-01

Proteins are inherently flexible at ambient temperature. At equilibrium, they are characterized by a set of conformations that undergo continuous exchange within a hierarchy of spatial and temporal scales ranging from nanometers to micrometers and femtoseconds to hours. Dynamic properties of proteins are essential for describing the structural bases of their biological functions including catalysis, binding, regulation and cellular structure. Nuclear magnetic resonance (NMR) spectroscopy represents a powerful technique for measuring these essential features of proteins. Here we provide an introduction to NMR-based approaches for studying protein dynamics, highlighting eight distinct methods with recent examples, contextualized within a common experimental and analytical framework. The selected methods are (1) Real-time NMR, (2) Exchange spectroscopy, (3) Lineshape analysis, (4) CPMG relaxation dispersion, (5) Rotating frame relaxation dispersion, (6) Nuclear spin relaxation, (7) Residual dipolar coupling, (8) Paramagnetic relaxation enhancement. PMID:21059410

Development of New Supramolecular Lyotropic Liquid Crystals and Their Application as Alignment Media for Organic Compounds.

PubMed

Leyendecker, Martin; Meyer, Nils-Christopher; Thiele, Christina M

2017-09-11

Most alignment media for the residual dipolar coupling (RDC) based molecular structure determination of small organic compounds consist of rod-like polymers dissolved in organic solvents or of swollen cross-linked polymer gels. Thus far, the synthesis of polymer-based alignment media has been a challenging process, which is often followed by a time-consuming sample preparation. We herein propose the use of non-polymeric alignment media based on benzenetricarboxamides (BTAs), which self-assemble into rod-like supramolecules. Our newly found supramolecular lyotropic liquid crystals (LLCs) are studied in terms of their LLC properties and their suitability as alignment media in NMR spectroscopy. Scalable enantiodifferentiating properties are introduced through a sergeant-and-soldier principle by blending achiral with chiral substituted BTAs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reconstruction of interatomic vectors by principle component analysis of nuclear magnetic resonance data in multiple alignments

NASA Astrophysics Data System (ADS)

Hus, Jean-Christophe; Bruschweiler, Rafael

2002-07-01

A general method is presented for the reconstruction of interatomic vector orientations from nuclear magnetic resonance (NMR) spectroscopic data of tensor interactions of rank 2, such as dipolar coupling and chemical shielding anisotropy interactions, in solids and partially aligned liquid-state systems. The method, called PRIMA, is based on a principal component analysis of the covariance matrix of the NMR parameters collected for multiple alignments. The five nonzero eigenvalues and their eigenvectors efficiently allow the approximate reconstruction of the vector orientations of the underlying interactions. The method is demonstrated for an isotropic distribution of sample orientations as well as for finite sets of orientations and internuclear vectors encountered in protein systems.

Vivaldi: visualization and validation of biomacromolecular NMR structures from the PDB.

PubMed

Hendrickx, Pieter M S; Gutmanas, Aleksandras; Kleywegt, Gerard J

2013-04-01

We describe Vivaldi (VIsualization and VALidation DIsplay; http://pdbe.org/vivaldi), a web-based service for the analysis, visualization, and validation of NMR structures in the Protein Data Bank (PDB). Vivaldi provides access to model coordinates and several types of experimental NMR data using interactive visualization tools, augmented with structural annotations and model-validation information. The service presents information about the modeled NMR ensemble, validation of experimental chemical shifts, residual dipolar couplings, distance and dihedral angle constraints, as well as validation scores based on empirical knowledge and databases. Vivaldi was designed for both expert NMR spectroscopists and casual non-expert users who wish to obtain a better grasp of the information content and quality of NMR structures in the public archive. Copyright © 2013 Wiley Periodicals, Inc.

Quantum Electric Dipole Lattice - Water Molecules Confined to Nanocavities in Beryl

NASA Astrophysics Data System (ADS)

Dressel, Martin; Zhukova, Elena S.; Thomas, Victor G.; Gorshunov, Boris P.

2018-02-01

Water is subject to intense investigations due to its importance in biological matter but keeps many of its secrets. Here, we unveil an even other aspect by confining H2O molecules to nanosize cages. Our THz and infrared spectra of water in the gemstone beryl evidence quantum tunneling of H2O molecules in the crystal lattice. The water molecules are spread out when confined in a nanocage. In combination with low-frequency dielectric measurements, we were also able to show that dipolar coupling among the H2O molecules leads towards a ferroelectric state at low temperatures. Upon cooling, a ferroelectric soft mode shifts through the THz range. Only quantum fluctuations prevent perfect macroscopic order to be fully achieved. Beside the significance to life science and possible application, nanoconfined water may become the prime example of a quantum electric dipolar lattice.

Modeling and simulation of magnetic resonance imaging based on intermolecular multiple quantum coherences

NASA Astrophysics Data System (ADS)

Cai, Congbo; Dong, Jiyang; Cai, Shuhui; Cheng, En; Chen, Zhong

2006-11-01

Intermolecular multiple quantum coherences (iMQCs) have many potential applications since they can provide interaction information between different molecules within the range of dipolar correlation distance, and can provide new contrast in magnetic resonance imaging (MRI). Because of the non-localized property of dipolar field, and the non-linear property of the Bloch equations incorporating the dipolar field term, the evolution behavior of iMQC is difficult to deduce strictly in many cases. In such cases, simulation studies are very important. Simulation results can not only give a guide to optimize experimental conditions, but also help analyze unexpected experimental results. Based on our product operator matrix and the K-space method for dipolar field calculation, the MRI simulation software was constructed, running on Windows operation system. The non-linear Bloch equations are calculated by a fifth-order Cash-Karp Runge-Kutta formulism. Computational time can be efficiently reduced by separating the effects of chemical shifts and strong gradient field. Using this software, simulation of different kinds of complex MRI sequences can be done conveniently and quickly on general personal computers. Some examples were given. The results were discussed.

Anomalous complete opaqueness in a sparse array of gold nanoparticle chains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bai Benfeng; Tsinghua-Foxconn Nanotechnology Research Center, Tsinghua University, Beijing 100084; Department of Physics and Mathematics, University of Eastern Finland, P.O. Box 111, FI-80101 Joensuu

2011-08-22

We report on an anomalous polarization-switching extinction effect in a sparse array of gold nanoparticle chains: under normal incidence of light, the array is almost transparent for one polarization; whereas it is fully opaque (with nearly zero transmittance) for the orthogonal polarization within a narrow band, even though the nanoparticles cover only a tiny fraction (say, 3.5%) of the transparent substrate surface. We reveal that the strong polarization-dependent short-range dipolar coupling and long-range radiative coupling of gold nanoparticles in this highly asymmetric array is responsible for this extraordinary effect.

Magnetosphere-Regolith/Exosphere Coupling: Differences and Similarities to the Earth Magnetosphere-Ionosphere Coupling

NASA Technical Reports Server (NTRS)

Gjerleov, J. W.; Slavin, J. A.

2001-01-01

Of the three Mercury passes made by Mariner 10, the first and third went through the Mercury magnetosphere. The third encounter which occurred during northward IMF (interplanetary magnetic field) showed quiet time magnetic fields. In contrast the third encounter observed clear substorm signatures including dipolarization, field-aligned currents (FACs) and injection of energetic electrons at geosynchronous orbit. However, the determined cross-tail potential drop and the assumed height integrated conductance indicate that the FAC should be 2-50 times weaker than observed. We address this inconsistency and the fundamental problem of FAC closure whether this takes place in the regolith or in the exosphere. The current state of knowledge of the magnetosphere-exosphere/regolith coupling is addressed and similarities and differences to the Earth magnetosphere-ionosphere coupling are discussed.

Modulating RNA Alignment Using Directional Dynamic Kinks: Application in Determining an Atomic-Resolution Ensemble for a Hairpin using NMR Residual Dipolar Couplings.

PubMed

Salmon, Loïc; Giambaşu, George M; Nikolova, Evgenia N; Petzold, Katja; Bhattacharya, Akash; Case, David A; Al-Hashimi, Hashim M

2015-10-14

Approaches that combine experimental data and computational molecular dynamics (MD) to determine atomic resolution ensembles of biomolecules require the measurement of abundant experimental data. NMR residual dipolar couplings (RDCs) carry rich dynamics information, however, difficulties in modulating overall alignment of nucleic acids have limited the ability to fully extract this information. We present a strategy for modulating RNA alignment that is based on introducing variable dynamic kinks in terminal helices. With this strategy, we measured seven sets of RDCs in a cUUCGg apical loop and used this rich data set to test the accuracy of an 0.8 μs MD simulation computed using the Amber ff10 force field as well as to determine an atomic resolution ensemble. The MD-generated ensemble quantitatively reproduces the measured RDCs, but selection of a sub-ensemble was required to satisfy the RDCs within error. The largest discrepancies between the RDC-selected and MD-generated ensembles are observed for the most flexible loop residues and backbone angles connecting the loop to the helix, with the RDC-selected ensemble resulting in more uniform dynamics. Comparison of the RDC-selected ensemble with NMR spin relaxation data suggests that the dynamics occurs on the ps-ns time scales as verified by measurements of R(1ρ) relaxation-dispersion data. The RDC-satisfying ensemble samples many conformations adopted by the hairpin in crystal structures indicating that intrinsic plasticity may play important roles in conformational adaptation. The approach presented here can be applied to test nucleic acid force fields and to characterize dynamics in diverse RNA motifs at atomic resolution.

Probing Na+ Induced Changes in the HIV-1 TAR Conformational Dynamics using NMR Residual Dipolar Couplings: New Insights into the Role of Counterions and Electrostatic Interactions in Adaptive Recognition†

PubMed Central

Casiano-Negroni, Anette; Sun, Xiaoyan; Al-Hashimi, Hashim M.

2012-01-01

Many regulatory RNAs undergo large changes in structure upon recognition of proteins and ligands but the mechanism by which this occur remains poorly understood. Using NMR residual dipolar coupling (RDCs), we characterized Na+ induced changes in the structure and dynamics of the bulge-containing HIV-1 transactivation response element (TAR) RNA that mirror changes induced by small molecules bearing a different number of cationic groups. Increasing the Na+ concentration from 25 mM to 320 mM led to a continuous reduction in the average inter-helical bend angle (from 46° to 22°), inter-helical twist angle (from 66° to −18°) and inter-helix flexibility (as measured by an increase in the internal generalized degree of order from 0.56 to 0.74). Similar conformational changes were observed with Mg2+, indicating that non-specific electrostatic interactions drive the conformational transition, although results also suggest that Na+ and Mg2+ may associate with TAR in distinct modes. The transition can be rationalized based on a population-weighted average of two ensembles comprising an electrostatically relaxed bent and flexible TAR conformation that is weakly associated with counterions, and a globally rigid coaxial conformation which has stronger electrostatic potential and association with counterions. The TAR inter-helical orientations that are stabilized by small molecules fall around the metal-induced conformational pathway, indicating that counterions may help predispose the TAR conformation for target recognition. Our results underscore the intricate sensitivity of RNA conformational dynamics to environmental conditions and demonstrate the ability to detect subtle conformational changes using NMR RDCs. PMID:17488097

Conformation analysis and molecular mobility of ethylene and tetrafluoroethylene copolymer using solid-state 19F MAS and 1H --> 19F CP/MAS NMR spectroscopy.

PubMed

Aimi, Keitaro; Ando, Shinji

2004-07-01

The changes in the conformation and molecular mobility accompanied by a phase transition in the crystalline domain were analyzed for ethylene (E) and tetrafluoroethylene (TFE) copolymer, ETFE, using variable-temperature (VT) solid-state 19F magic angle spinning (MAS) and 1H --> 19F cross-polarization (CP)/MAS NMR spectroscopy. The shifts of the signals for fluorines in TFE units to higher frequency and the continuing decrease and increase in the T1rho(F) values suggest that conformational exchange motions exist in the crystalline domain between 42 and 145 degrees C. Quantum chemical calculations of magnetic shielding constants showed that the high-frequency shift of TFE units should be induced by trans to gauche conformational changes at the CH2-CF2 linkage in the E-TFE unit. Although the 19F signals of the crystalline domain are substantially overlapped with those of the amorphous domain at ambient probe temperature (68 degrees C), they were successfully distinguished by using the dipolar filter and spin-lock pulse sequences at 145 degrees C. The dipolar coupling constants for the crystalline domain, which can be estimated by fitting the dipolar oscillation behaviors in the 1H --> 19F CP curve, showed a significant decrease with increasing temperature from 42 to 145 degrees C. This is due to the averaging of 1H-19F dipolar interactions originating from the molecular motion in the crystalline domain. The increase in molecular mobility in the crystalline domain was clearly shown by VT T1rho(F) and 1H --> 19F CP measurements in the phase transition temperature range. Copyright 2004 John Wiley & Sons, Ltd.

Back-clocking of Fe2+/Fe1+ spin states in a H2-producing catalyst by advanced EPR

NASA Astrophysics Data System (ADS)

Stathi, Panagiota; Mitrikas, George; Sanakis, Yiannis; Louloudi, Maria; Deligiannakis, Yiannis

2013-10-01

A mononuclear Fe-(P(PPh2)3) ((P(PPh2)3) = tris[2-diphenylphospino)ethyl]phosphine) catalyst was studied in situ under catalytic conditions using advanced electron paramagnetic resonance (EPR) techniques. Fe-(P(PPh2)3) efficiently catalyses H2 production using HCOOH as substrate. Dual-mode continuous-wave (CW) EPR, used to study the initial Fe2+(S = 2) state, shows that the complex is characterised by a - rather small - zero field splitting parameter Δ = 0.45 cm-1 and geff = 8.0. In the presence of HCOOH substrate the complex evolves and a unique Fe1+(S = 1/2) state is trapped. The Fe1+ atom is coordinated by four 31P nuclei in a pseudo-C3 symmetry. Only a small fraction of the Fe1+ spin density is delocalised onto the 31P atoms. Four-pulse electron spin echo envelope modulation (ESEEM) and two-dimensional hyperfine sublevel correlation spectroscopy (2D-HYSCORE) data reveal the existence of two types of 1H couplings. One corresponds to weak, purely dipolar coupling, tentatively assigned to phenyl protons. The most important is a - rather unusual - 1H coupling with negative Aiso (-2.75 MHz) and strong dipolar part (T = 5.5 MHz). This 1H is located on the pseudo-C3 symmetry axis of the Fe1+-(P(PPh2)3-HCOO- complex where one substrate molecule, formate anion, is coordinated on the Fe1+ atom.

Two-dimensional solitons in dipolar Bose-Einstein condensates with spin-orbit coupling

NASA Astrophysics Data System (ADS)

Jiang, Xunda; Fan, Zhiwei; Chen, Zhaopin; Pang, Wei; Li, Yongyao; Malomed, Boris A.

2016-02-01

We report families of two-dimensional (2D) composite solitons in spinor dipolar Bose-Einstein condensates, with two localized components linearly mixed by the spin-orbit coupling (SOC), and the intrinsic nonlinearity represented by the dipole-dipole interaction (DDI) between atomic magnetic moments polarized in plane by an external magnetic field. Recently, stable solitons were predicted in the form of semivortices (composites built of coupled fundamental and vortical components) in the 2D system combining the SOC and contact attractive interactions. Replacing the latter by the anisotropic long-range DDI, we demonstrate that, for a fixed norm of the soliton, the system supports a continuous family of stable spatially asymmetric vortex solitons (AVSs), parameterized by an offset of the pivot of the vortical component relative to its fundamental counterpart. The offset is limited by a certain maximum value, while the energy of the AVS practically does not depend on the offset. At small values of the norm, the vortex solitons are subject to a weak oscillatory instability. In the present system, with the Galilean invariance broken by the SOC, the composite solitons are set in motion by a kick the strength of which exceeds a certain depinning value. The kicked solitons feature a negative effective mass, drifting along a spiral trajectory opposite to the direction of the kick. A critical angular velocity, up to which the semivortices may follow rotation of the polarizing magnetic field, is found too.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Majetich, Sara

In the proposed research program we will investigate the time- and frequency-dependent behavior of ordered nanoparticle assemblies, or nanoparticle crystals. Magnetostatic interactions are long-range and anisotropic, and this leads to complex behavior in nanoparticle assemblies, particularly in the time- and frequency-dependent properties. We hypothesize that the high frequency performance of composite materials has been limited because of the range of relaxation times; if a composite is a dipolar ferromagnet at a particular frequency, it should have the advantages of a single phase material, but without significant eddy current power losses. Arrays of surfactant-coated monodomain magnetic nanoparticles can exhibit long-range magneticmore » order that is stable over time. The magnetic domain size and location of domain walls is governed not by structural grain boundaries but by the shape of the array, due to the local interaction field. Pores or gaps within an assembly pin domain walls and limit the domain size. Measurements of the magnetic order parameter as a function of temperature showed that domains can exist at high temoerature, and that there is a collective phase transition, just as in an exchange-coupled ferromagnet. Dipolar ferromagnets are not merely of fundamental interest; they provide an interesting alternative to exchange-based ferromagnets. Dipolar ferromagnets made with high moment metallic particles in an insulating matrix could have high permeability without large eddy current losses. Such nanocomposites could someday replace the ferrites now used in phase shifters, isolators, circulators, and filters in microwave communications and radar applications. We will investigate the time- and frequency-dependent behavior of nanoparticle crystals with different magnetic core sizes and different interparticle barrier resistances, and will measure the magnetic and electrical properties in the DC, low frequency (0.1 Hz - 1 kHz), moderate frequency (10 Hz - 500 MHz), and high frequency (up to 20 GHz) regimes. Our results will demonstrate whether a DC dipolar ferromagnet shows collective frequency-dependent reponse similar to that of an exchange-based ferromagnet, and will provide data for comparison of optimal nanocomposite properties with those of ferrites used in high frequency applications. Both the magnetic and electronic response of the composites will be examined in order to determine the frequency range where hopping conductivity leads to significant eddy current power losses. In the high frequency regime we will look for evidence of spin wave quantization and the resulting decrease in non-linear spin wave processes that could affect the performance of high frequency magnetic devices.« less

New metal phthalocyanines/metal simple hydroxide multilayers: experimental evidence of dipolar field-driven magnetic behavior.

PubMed

Bourzami, Riadh; Eyele-Mezui, Séraphin; Delahaye, Emilie; Drillon, Marc; Rabu, Pierre; Parizel, Nathalie; Choua, Sylvie; Turek, Philippe; Rogez, Guillaume

2014-01-21

A series of new hybrid multilayers has been synthesized by insertion-grafting of transition metal (Cu(II), Co(II), Ni(II), and Zn(II)) tetrasulfonato phthalocyanines between layers of Cu(II) and Co(II) simple hydroxides. The structural and spectroscopic investigations confirm the formation of new layered hybrid materials in which the phthalocyanines act as pillars between the inorganic layers. The magnetic investigations show that all copper hydroxide-based compounds behave similarly, presenting an overall antiferromagnetic behavior with no ordering down to 1.8 K. On the contrary, the cobalt hydroxide-based compounds present a ferrimagnetic ordering around 6 K, regardless of the nature of the metal phthalocyanine between the inorganic layers. The latter observation points to strictly dipolar interactions between the inorganic layers. The amplitude of the dipolar field has been evaluated from X-band and Q-band EPR spectroscopy investigation (Bdipolar ≈ 30 mT).

Dipolar filtered magic-sandwich-echoes as a tool for probing molecular motions using time domain NMR

NASA Astrophysics Data System (ADS)

Filgueiras, Jefferson G.; da Silva, Uilson B.; Paro, Giovanni; d'Eurydice, Marcel N.; Cobo, Márcio F.; deAzevedo, Eduardo R.

2017-12-01

We present a simple 1 H NMR approach for characterizing intermediate to fast regime molecular motions using 1 H time-domain NMR at low magnetic field. The method is based on a Goldmann Shen dipolar filter (DF) followed by a Mixed Magic Sandwich Echo (MSE). The dipolar filter suppresses the signals arising from molecular segments presenting sub kHz mobility, so only signals from mobile segments are detected. Thus, the temperature dependence of the signal intensities directly evidences the onset of molecular motions with rates higher than kHz. The DF-MSE signal intensity is described by an analytical function based on the Anderson Weiss theory, from where parameters related to the molecular motion (e.g. correlation times and activation energy) can be estimated when performing experiments as function of the temperature. Furthermore, we propose the use of the Tikhonov regularization for estimating the width of the distribution of correlation times.

Impact of electronic coupling, symmetry, and planarization on one- and two-photon properties of triarylamines with one, two, or three diarylboryl acceptors.

PubMed

Makarov, Nikolay S; Mukhopadhyay, Sukrit; Yesudas, Kada; Brédas, Jean-Luc; Perry, Joseph W; Pron, Agnieszka; Kivala, Milan; Müllen, Klaus

2012-04-19

We have performed a study of the one- and two-photon absorption properties of a systematically varied series of triarylamino-compounds with one, two, or three attached diarylborane arms arranged in linear dipolar, bent dipolar, and octupolar geometries. Two-photon fluorescence excitation spectra were measured over a wide spectral range with femtosecond laser pulses. We found that on going from the single-arm to the two- and three-arm systems, the peak in two-photon absorption (2PA) cross-section is suppressed by factors of 3-11 for the lowest excitonic level associated with the electronic coupling of the arms, whereas it is enhanced by factors of 4-8 for the higher excitonic level. These results show that the coupling of arms redistributes the 2PA cross-section between the excitonic levels in a manner that strongly favors the higher-energy excitonic level. The experimental data on one- and two-photon cross-sections, ground- and excited-state transition dipole moments, and permanent dipole moment differences between the ground and the lowest excited states were compared to the results obtained from a simple Frenkel exciton model and from highly correlated quantum-chemical calculations. It has been found that planarization of the structure around the triarylamine moiety leads to a sizable increase in peak 2PA cross-section for the lowest excitonic level of the two-arm system, whereas for the three-arm system, the corresponding peak was weakened and shifted to lower energy. Our studies show the importance of the interarm coupling, number of arms, and structural planarity on both the enhancement and the suppression of two-photon cross-sections in multiarm molecules. © 2012 American Chemical Society

How to tackle protein structural data from solution and solid state: An integrated approach.

PubMed

Carlon, Azzurra; Ravera, Enrico; Andrałojć, Witold; Parigi, Giacomo; Murshudov, Garib N; Luchinat, Claudio

2016-02-01

Long-range NMR restraints, such as diamagnetic residual dipolar couplings and paramagnetic data, can be used to determine 3D structures of macromolecules. They are also used to monitor, and potentially to improve, the accuracy of a macromolecular structure in solution by validating or "correcting" a crystal model. Since crystal structures suffer from crystal packing forces they may not be accurate models for the macromolecular structures in solution. However, the presence of real differences should be tested for by simultaneous refinement of the structure using both crystal and solution NMR data. To achieve this, the program REFMAC5 from CCP4 was modified to allow the simultaneous use of X-ray crystallographic and paramagnetic NMR data and/or diamagnetic residual dipolar couplings. Inconsistencies between crystal structures and solution NMR data, if any, may be due either to structural rearrangements occurring on passing from the solution to solid state, or to a greater degree of conformational heterogeneity in solution with respect to the crystal. In the case of multidomain proteins, paramagnetic restraints can provide the correct mutual orientations and positions of domains in solution, as well as information on the conformational variability experienced by the macromolecule. Copyright © 2016 Elsevier B.V. All rights reserved.

Silyl Glyoxylates. Conception and Realization of Flexible Conjunctive Reagents for Multicomponent Coupling

PubMed Central

Boyce, Gregory R.; Greszler, Stephen N.; Linghu, Xin; Malinowski, Justin T.; Nicewicz, David A.; Satterfield, Andrew D.; Schmitt, Daniel C.; Steward, Kimberly M.

2012-01-01

This Perspective describes the discovery and development of silyl glyoxylates, a new family of conjunctive reagents for use in multicomponent coupling reactions. The selection of the nucleophilic and electrophilic components determines whether the silyl glyoxylate reagent will function as a synthetic equivalent to the dipolar glycolic acid synthon, the glyoxylate anion synthon, or the α-keto ester homoenolate synthon. The ability to select for any of these reaction modes has translated to excellent structural diversity in the derived three- and four-component coupling adducts. Preliminary findings on the development of catalytic reactions using these reagents are detailed, as are the design and discovery of new reactions directed toward particular functional group arrays embedded within bioactive natural products. PMID:22414181

Giant Electrocaloric Effect in Ferroelectrics with Tailored Polaw-Nanostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Qiming

2015-06-24

Electrocaloric effect (ECE) is the temperature and/or entropy change in a dielectric material caused by an electric field induced polarization change. Although ECE has been studied since 1930s, the very small ECE observed in earlier studies in bulk materials before 2007 makes it not attractive for practical cooling applications. The objectives of this DOE program are to carry out a systematical scientific research on the entropy change and ECE in polar-dielectrics, especially ferroelectrics based on several fundamental hypotheses and to search for answers on a few scientific questions. Especially, this research program developed a series of polar-dielectric materials with controlledmore » nano- and meso-structures and carried out studies on how these structures affect the polar-ordering, correlations, energy landscapes, and consequently the entropy states at different phases and ECE. The key hypotheses of the program include: (i) Whether a large ECE can be obtained near the ferroelectric-paraelectric (FE-PE) transition in properly designed ferroelectrics which possess large polarization P and large ß (the coefficient in the thermodynamic Landau theory where the Gibbs free energy G = G = G 0+ ½ a P 2 +1/4 b P 4 + 1/6 c P 6 – EP, and a = ß (T-T c), where b,c,ß and Tc are constants)? (ii) What determines/determine ß? Whether a ferroelectric material with built-in disorders, which disrupt the polar-correlations and enabling a large number of local polar-states, such as a properly designed ferroelectric relaxor, can achieve a large ECE? (iii) How to design a ferroelectric material which has flat energy landscape so that the energy barriers for switching among different phases are vanishingly small? What are the necessary conditions to maximize the number of coexisting phases? (iv) How to design ferroelectric materials with a large tunable dielectric response? That is, at zero electric field, the material possesses very low polar-correlation and hence a very small dielectric constant, under the application of electric field, the material develops long range polar-correlation and hence a high dielectric response. Studying and developing these materials will deepen our understanding on the polarization responses in strongly coupled materials and the roles of molecular and nano, meso-, and micro-scale defects and structures on the polarization responses. On the application front, besides ECE, these dielectrics will also have great impact on micro-electronics and communications. (v) The multi-field effect, besides the electric, elastic and even magnetic effects, could be made use of to tune the energy landscape of polar-materials and hence enhance the ECE. Hence the question is what are the suitable material systems to develop and maximize the multi-field effects? (vi) Besides solid dielectric, liquid dielectrics with properly designed molecular structures and dipolar coupling can also exhibit a large ECE near the dipolar order-disorder transition. The study of order-disorder transition and their influence on entropy change and ECE will provide additional avenue to study dielectrics and understand relationship between the polar-ordering and dipolar entropy in dielectrics. (vii) Besides the regular ECE in which applying an electric field will induce dipolar ordering, there are dielectric material systems which can exhibit negative ECE in which the applied field will reduce the dipolar ordering and anomalous ECE in which applying an electric field pulse will generate cooling only. The question is how to control and balance the nano- and meso-scale polar coupling in dielectrics to achieve such effects? ECE in dielectrics provides an interesting and effective avenue to probe the polar-correlation in dielectrics. Thus the study of ECE in polar-dielectrics, besides the application values, will also deepen our understanding of strongly coupled materials systems, phase transitions, and materials systems with nano- and meso-scale disorders. Through the efforts of this DoE program, we have developed understandings for many questions and materials approaches for many hypotheses listed above. The major accomplishments include: (i) The first one to show that a giant ECE can be obtained in bulk materials of ferroelectric P(VDF-TrFE) copolymer, which has a large ß coefficient and high polarization, near FE-PE transition.[1,3,12] (ii) The first who developed the theoretical analyses on the upper bound of dipolar entropy change in polar-materials and the general approach to maximize the coexisting phases with vanishingly small switching fields among the coexisting phases[10,23] Experimental results confirm these theoretical predictions.[24] (iii) The first to show that the relaxor ferroelectrics, due to built-in defects structures at nano- and meso scale, exhibit a giant ECE over a broad temperature range.[1,3,7,14] (iv) The first to show that a large ECE can be obtained near order-disorder transition in dielectric fluids such as liquid crystals with large dielectric anisotropy. Also the study developed a general approach for developing dielectric fluids to achieve a large electric field induced entropy change.[26] (v) We are starting to explore the multi-field effect (multiferroic effect) in nanocomposites in which there exist large dielectric contrasts between the matrix and nanofilelrs and showed that a significantly enhanced ECE compared with polymer matrix.[36] (vi) By facially tuning the nano- and meso-scale dipolar coupling, we are the first to show that an anomalous ECE can be obtained in a relaxor/normal ferroelectric blend.[39] (vii) Introduced and demonstrated that the internal bias field approach can be effective in enhancing the EC response at low electric field. The result is significant since for practical applications, a low applied field is highly desired. (viii) A high sensitivity ECE characterization system has been developed. This program has made major contributions to the advancement of the EC materials and understandings of EC phenomena. To reflect the advancement in the EC materials development and scientific understandings on ECE through in this time period (from Sept. 1, 2007 to May 2015), this final report is written based on the reports complied each year through the program. Some early works on the ECE which were obtained using the indirect method are not included in this report.« less

Response of energetic particles to local magnetic dipolarization inside geosynchronous orbit

NASA Astrophysics Data System (ADS)

Motoba, T.; Ohtani, S.; Gkioulidou, M.; Takahashi, K.

2017-12-01

Magnetic field dipolarization and energetic particle injections are the most distinct phenomena observed in the inner magnetosphere during the substorm expansion phase. Compared to a wealth of knowledge about the phenomenology of magnetic dipolarizations and particle injections at/outside geosynchronous orbit (GEO), our understanding of them inside GEO remains incomplete because of a very limited number of previous studies. In the present study, we statistically examine the response of 1-1000 keV energetic particles to local magnetic dipolarization by performing a superposed epoch analysis of energetic particle fluxes with the zero epoch defined as the dipolarization onset times. Based on data from the Van Allen Probes tail seasons in 2012-2016, we identified a total of 97 magnetic dipolarization events which occurred closer to the magnetic equator (i.e., BH, which is antiparallel to the Earth's dipole axis, is the dominant component of the local magnetic field at least for 5 min before the onset). For major ion species (hydrogen, helium, and oxygen ions), the relative flux intensity to the pre-onset level increases at > 50 keV and decreases at < 30 keV. The hydrogen and helium ion fluxes in the hundreds of keV range sharply increase within a minute after the onset and then decay. Compared to the short-lived nature of hydrogen and helium ion flux enhancements, oxygen ion fluxes are enhanced more gradually (on the order of several minutes). The relative ion flux intensity and peak energy generally tend to increase for stronger dipolarization-related impulsive westward electric field. This suggests that the impulsive electric field is responsible for the energization and/or transport of energetic ions inside GEO. On the other hand, the electron flux enhancement first appears from several tens of keV to a few hundreds of keV, and then exhibits an inverse energy dispersion. For dipolarizations with strong impulsive westward electric fields, the relative electron flux intensity increases up to 5-10 times, in particular most significant at several tens of keV. This result suggests that the impulsive electric field acts as an efficient factor in the rapid energization of the tens-of-keV electrons. We also discuss how the response of energetic particles to dipolarization depends on MLT, radial distance, and pitch angle.

The Plasma Sheet as Natural Symmetry Plane for Dipolarization Fronts in the Earth's Magnetotail

NASA Astrophysics Data System (ADS)

Frühauff, D.; Glassmeier, K.-H.

2017-11-01

In this work, observations of multispacecraft mission Time History of Events and Macroscale Interactions during Substorms are used for statistical investigation of dipolarization fronts in the near-Earth plasma sheet of the magnetotail. Using very stringent criteria, 460 events are detected in almost 10 years of mission data. Minimum variance analysis is used to determine the normal directions of the phase fronts, providing evidence for the existence of a natural symmetry of these phenomena, given by the neutral sheet of the magnetotail. This finding enables the definition of a local coordinate system based on the Tsyganenko model, reflecting the intrinsic orientation of the neutral sheet and, therefore, the dipolarization fronts. In this way, the comparison of events with very different background conditions is improved. Through this study, the statistical results of Liu, Angelopoulos, Runov, et al. (2013) are both confirmed and extended. In a case study, the knowledge of this plane of symmetry helps to explain the concave curvature of dipolarization fronts in the XZ plane through phase propagation speeds of magnetoacoustic waves. A second case study is presented to determine the central current system of a passing dipolarization front through a constellation of three spacecraft. With this information, a statistical analysis of spacecraft observations above and below the neutral sheet is used to provide further evidence for the neutral sheet as the symmetry plane and the central current system. Furthermore, it is shown that the signatures of dipolarization fronts are under certain conditions closely related to that of flux ropes, indicating a possible relationship between these two transient phenomena.

Optically induced circular and axial birefringences in achiral fluids: an ab initio study of the optical Faraday effect

NASA Astrophysics Data System (ADS)

Baranowska, Angelika; Rizzo, Antonio; Coriani, Sonia

2006-07-01

A computational analysis of the effects (intensity-dependent change in the refractive index and the optical Faraday effect, OFE) induced in an achiral fluid by circularly polarized, linearly polarized or unpolarized light is presented. The connection between the molecular parameters appearing in the expression of the observable, as derived by Woźniak in the 1990s, and the appropriate linear and cubic frequency dependent response functions is made for the general case of both chiral and non-chiral fluid. The parameters which are non-vanishing in the case of achiral systems are then computed employing a coupled cluster singles and doubles wave function model and a wide choice of correlation consistent basis sets, for a set of reference systems, including a rare gas (neon), a non-dipolar (N2) and a dipolar (CO) molecule. Contributions due to magnetic and quadrupolar interactions between the fields and the gases are neglected, since they are in principle of much less importance than the purely electric dipolar interactions. Nevertheless a rough estimate of their size is given. The aim of the study is to assess the detectability of OFE. To this end, the ab initio results are compared with those obtained in this work for the closely related optical Kerr effect (OKE) and with those yielded by the classical Faraday effect.

Polarized neutron reflectivity from monolayers of self-assembled magnetic nanoparticles.

PubMed

Mishra, D; Petracic, O; Devishvili, A; Theis-Bröhl, K; Toperverg, B P; Zabel, H

2015-04-10

We prepared monolayers of iron oxide nanoparticles via self-assembly on a bare silicon wafer and on a vanadium film sputter deposited onto a plane sapphire substrate. The magnetic configuration of nanoparticles in such a dense assembly was investigated by polarized neutron reflectivity. A theoretical model fit shows that the magnetic moments of nanoparticles form quasi domain-like configurations at remanence. This is attributed to the dipolar coupling amongst the nanoparticles.

Resonance coupling in plasmonic nanomatryoshka homo- and heterodimers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahmadivand, Arash, E-mail: aahma011@fiu.edu; Sinha, Raju; Pala, Nezih

Here, we examine the electromagnetic (EM) energy coupling and hybridization of plasmon resonances between closely spaced concentric nanoshells known as “nanomatryoshka” (NM) units in symmetric and antisymmetric compositions using the Finite Difference Time Domain (FDTD) analysis. Utilizing plasmon hybridization model, we calculated the energy level diagrams and verified that, in the symmetric dimer (in-phase mode in a homodimer), plasmonic bonding modes are dominant and tunable within the considered bandwidth. In contrast, in the antisymmetric dimer (out-of-phase mode in a heterodimer), due to the lack of the geometrical symmetry, new antibonding modes appear in the extinction profile, and this condition givesmore » rise to repeal of dipolar field coupling. We also studied the extinction spectra and positions of the antibonding and bonding modes excited due to the energy coupling between silver and gold NM units in a heterodimer structure. Our analysis suggest abnormal shifts in the higher energy modes. We propose a method to analyze the behavior of multilayer concentric nanoshell particles in an antisymmetric orientation employing full dielectric function calculations and the Drude model based on interband transitions in metallic components. This study provides a method to predict the behavior of the higher energy plasmon resonant modes in entirely antisymmetric structures such as compositional heterodimers.« less

Some Surprising Implications of NMR-directed Simulations of Substrate Recognition and Binding by Cytochrome P450cam (CYP101A1).

PubMed

Asciutto, Eliana K; Pochapsky, Thomas C

2018-04-27

Cytochrome P450 cam (CYP101A1) catalyzes the stereospecific 5-exo hydroxylation of d-camphor by molecular oxygen. Previously, residual dipolar couplings measured for backbone amide 1 H- 15 N correlations in both substrate-free and bound forms of CYP101A1 were used as restraints in soft annealing molecular dynamic simulations in order to identify average conformations of the enzyme with and without substrate bound. Multiple substrate-dependent conformational changes remote from the enzyme active site were identified, and site-directed mutagenesis and activity assays confirmed the importance of these changes in substrate recognition. The current work makes use of perturbation response scanning (PRS) and umbrella sampling molecular dynamic of the residual dipolar coupling-derived CYP101A1 structures to probe the roles of remote structural features in enforcing the regio- and stereospecific nature of the hydroxylation reaction catalyzed by CYP101A1. An improper dihedral angle Ψ was defined and used to maintain substrate orientation in the CYP101A1 active site, and it was observed that different values of Ψ result in different PRS response maps. Umbrella sampling methods show that the free energy of the system is sensitive to Ψ, and bound substrate forms an important mechanical link in the transmission of mechanical coupling through the enzyme structure. Finally, a qualitative approach to interpreting PRS maps in terms of the roles of secondary structural features is proposed. Copyright © 2018 Elsevier Ltd. All rights reserved.

Laboratory Study of Wave Generation Near Dipolarization Fronts

NASA Astrophysics Data System (ADS)

Tejero, E. M.; Enloe, C. L.; Amatucci, B.; Crabtree, C. E.; Ganguli, G.; Malaspina, D.

2017-12-01

Experiments conducted in the Space Physics Simulation Chamber at the Naval Research Laboratory (NRL) create plasma equilibria that replicate those found in dipolarization fronts. These experiments were designed to study the dynamics of boundary layers, such as dipolarization fronts, and it was found that there are instabilities generated by highly inhomogeneous plasma flows. It has previously been shown that these highly inhomogeneous flows can generate waves in the lower hybrid frequency range. Analysis of satellite observations indicate that the sheared flows are a plausible explanation for the observed lower hybrid waves at dipolarization fronts since they can generate longer wavelengths compared to the electron gyroradius, which is consistent with observations. Recent experiments at NRL have demonstrated that these flows can also generate electromagnetic waves in the whistler band. These waves are large amplitude, bursty waves that exhibit frequency chirps similar to whistler mode chorus. Recent results from these experiments and comparisons to in situ observations will be presented. * Work supported by the Naval Research Laboratory Base Program and NASA Grant No. NNH17AE70I.

Quantum Landau damping in dipolar Bose-Einstein condensates

NASA Astrophysics Data System (ADS)

Mendonça, J. T.; Terças, H.; Gammal, A.

2018-06-01

We consider Landau damping of elementary excitations in Bose-Einstein condensates (BECs) with dipolar interactions. We discuss quantum and quasiclassical regimes of Landau damping. We use a generalized wave-kinetic description of BECs which, apart from the long-range dipolar interactions, also takes into account the quantum fluctuations and the finite-energy corrections to short-range interactions. Such a description is therefore more general than the usual mean-field approximation. The present wave-kinetic approach is well suited for the study of kinetic effects in BECs, such as those associated with Landau damping, atom trapping, and turbulent diffusion. The inclusion of quantum fluctuations and energy corrections changes the dispersion relation and the damping rates, leading to possible experimental signatures of these effects. Quantum Landau damping is described with generality, and particular examples of dipolar condensates in two and three dimensions are studied. The occurrence of roton-maxon excitations, and their relevance to Landau damping, are also considered in detail. The present approach is mainly based on a linear perturbative procedure, but the nonlinear regime of Landau damping, which includes atom trapping and atom diffusion, is also briefly discussed.

Nuclear magnetic resonance signal dynamics of liquids in the presence of distant dipolar fields, revisited

PubMed Central

Barros, Wilson; Gochberg, Daniel F.; Gore, John C.

2009-01-01

The description of the nuclear magnetic resonance magnetization dynamics in the presence of long-range dipolar interactions, which is based upon approximate solutions of Bloch–Torrey equations including the effect of a distant dipolar field, has been revisited. New experiments show that approximate analytic solutions have a broader regime of validity as well as dependencies on pulse-sequence parameters that seem to have been overlooked. In order to explain these experimental results, we developed a new method consisting of calculating the magnetization via an iterative formalism where both diffusion and distant dipolar field contributions are treated as integral operators incorporated into the Bloch–Torrey equations. The solution can be organized as a perturbative series, whereby access to higher order terms allows one to set better boundaries on validity regimes for analytic first-order approximations. Finally, the method legitimizes the use of simple analytic first-order approximations under less demanding experimental conditions, it predicts new pulse-sequence parameter dependencies for the range of validity, and clarifies weak points in previous calculations. PMID:19425789

Role of the antiferromagnetic pinning layer on spin wave properties in IrMn/NiFe based spin-valves

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gubbiotti, G., E-mail: gubbiotti@fisica.unipg.it; Tacchi, S.; Del Bianco, L.

2015-05-07

Brillouin light scattering (BLS) was exploited to study the spin wave properties of spin-valve (SV) type samples basically consisting of two 5 nm-thick NiFe layers (separated by a Cu spacer of 5 nm), differently biased through the interface exchange coupling with an antiferromagnetic IrMn layer. Three samples were investigated: a reference SV sample, without IrMn (reference); one sample with an IrMn underlayer (10 nm thick) coupled to the bottom NiFe film; one sample with IrMn underlayer and overlayer of different thickness (10 nm and 6 nm), coupled to the bottom and top NiFe film, respectively. The exchange coupling with the IrMn, causing the insurgence ofmore » the exchange bias effect, allowed the relative orientation of the NiFe magnetization vectors to be controlled by an external magnetic field, as assessed through hysteresis loop measurements by magneto-optic magnetometry. Thus, BLS spectra were acquired by sweeping the magnetic field so as to encompass both the parallel and antiparallel alignment of the NiFe layers. The BLS results, well reproduced by the presented theoretical model, clearly revealed the combined effects on the spin dynamic properties of the dipolar interaction between the two NiFe films and of the interface IrMn/NiFe exchange coupling.« less

Indirect measurement of N-14 quadrupolar coupling for NH3 intercalated in potassium graphite

NASA Technical Reports Server (NTRS)

Tsang, T.; Fronko, R. M.; Resing, H. A.

1987-01-01

A method for indirect measurement of the nuclear quadrupolar coupling was developed and applied to NH3 molecules in the graphite intercalation compound K(NH3)4.3C24, which has a layered structure with alternating carbon and intercalant layers. Three triplets were observed in the H-1 NMR spectra of the compound. The value of the N-14 quadrupolar coupling constant of NH3 (3.7 MHz), determined indirectly from the H-1 NMR spectra, was intermediate between the gas value of 4.1 MHz and the solid-state value of 3.2 MHz. The method was also used to deduce the (H-1)-(H-1) and (N-14)-(H-1) dipolar interactions, the H-1 chemical shifts, and the molecular orientations and motions of NH3.

Toroidal resonance based optical modulator employing hybrid graphene-dielectric metasurface.

PubMed

Liu, Gui-Dong; Zhai, Xiang; Xia, Sheng-Xuan; Lin, Qi; Zhao, Chu-Jun; Wang, Ling-Ling

2017-10-16

In this paper, we demonstrate the combination of a dielectric metasurface with a graphene layer to realize a high performance toroidal resonance based optical modulator. The dielectric metasurface consists of two mirrored asymmetric silicon split-ring resonators (ASSRRs) that can support strong toroidal dipolar resonance with narrow line width (~0.77 nm) and high quality (Q)-factor (~1702) and contrast ratio (~100%). Numerical simulation results show that the transmission amplitude of the toroidal dipolar resonance can be efficiently modulated by varying the Fermi energy EF when the graphene layer is integrated with the dielectric metasurface, and a max transmission coefficient difference up to 78% is achieved indicating that the proposed hybrid graphene/dielectric metasurface shows good performance as an optical modulator. The effects of the asymmetry degree of the ASSRRs on the toroidal dipolar resonance are studied and the efficiency of the transmission amplitude modulation of graphene is also investigated. Our results may also provide potential applications in optical filter and bio-chemical sensing.

Multi-scale multi-point observation of dipolarization in the near-Earth's magnetotail

NASA Astrophysics Data System (ADS)

Nakamura, R.; Varsani, A.; Genestreti, K.; Nakamura, T.; Baumjohann, W.; Birn, J.; Le Contel, O.; Nagai, T.

2017-12-01

We report on evolution of the dipolarization in the near-Earth plasma sheet during two intense substorms based on observations when the four spacecraft of the Magnetospheric Multiscale (MMS) together with GOES and Geotail were located in the near Earth magnetotail. These multiple spacecraft together with the ground-based magnetogram enabled to obtain the location of the large- scale substorm current wedge (SCW) and overall changes in the plasma sheet configuration. MMS was located in the southern hemisphere at the outer plasma sheet and observed fast flow disturbances associated with dipolarizations. The high time-resolution measurements from MMS enable us to detect the rapid motion of the field structures and the flow disturbances separately and to resolve signatures below the ion-scales. We found small-scale transient field-aligned current sheets associated with upward streaming cold plasmas and Hall-current layers in the fast flow shear region. Observations of these current structures are compared with simulations of reconnection jets.

Relative merits of rCW(A) and XiX heteronuclear spin decoupling in solid-state magic-angle-spinning NMR spectroscopy: A bimodal Floquet analysis.

PubMed

Equbal, Asif; Leskes, Michal; Nielsen, Niels Chr; Madhu, P K; Vega, Shimon

2016-02-01

We present a bimodal Floquet analysis of the recently introduced refocused continuous wave (rCW) solid-state NMR heteronuclear dipolar decoupling method and compare it with the similar looking X-inverse X (XiX) scheme. The description is formulated in the rf interaction frame and is valid for both finite and ideal π pulse rCW irradiation that forms the refocusing element in the rCW scheme. The effective heteronuclear dipolar coupling Hamiltonian up to first order is described. The analysis delineates the difference between the two sequences to different orders of their Hamiltonians for both diagonal and off-diagonal parts. All the resonance conditions observed in experiments and simulations have been characterised and their influence on residual line broadening is highlighted. The theoretical comparison substantiates the numerical simulations and experimental results to a large extent. Copyright © 2016 Elsevier Inc. All rights reserved.

Single array of magnetic vortex disks uses in-plane anisotropy to create different logic gates

NASA Astrophysics Data System (ADS)

Vigo-Cotrina, H.; Guimarães, A. P.

2017-11-01

Using micromagnetic simulation, we show that in-plane uniaxial magnetic anisotropy (IPUA) can be used to obtain FAN-OUT, AND and OR gates in an array of coupled disks with magnetic vortex configuration. First, we studied the influence of the direction of application of the IPUA on the energy transfer time (τ) between two identical coupled nanodisks. We found that when the direction of the IPUA is along the x axis the magnetic interaction increases, allowing shorter values of τ , while the IPUA along the y direction has the opposite effect. The magnetic interactions between the nanodisks along x and y directions (the coupling integrals) as a function of the uniaxial anisotropy constant (Kσ) were obtained using a simple dipolar model. Next, we demonstrated that choosing a suitable direction of application of the IPUA, it is possible to create several different logic gates with a single array of coupled nanodisks.

Energetic Electron Acceleration and Injection During Dipolarization Events in Mercury's Magnetotail

NASA Astrophysics Data System (ADS)

Dewey, Ryan M.; Slavin, James A.; Raines, Jim M.; Baker, Daniel N.; Lawrence, David J.

2017-12-01

Energetic particle bursts associated with dipolarization events within Mercury's magnetosphere were first observed by Mariner 10. The events appear analogous to particle injections accompanying dipolarization events at Earth. The Energetic Particle Spectrometer (3 s resolution) aboard MESSENGER determined the particle bursts are composed entirely of electrons with energies ≳ 300 keV. Here we use the Gamma-Ray Spectrometer high-time-resolution (10 ms) energetic electron measurements to examine the relationship between energetic electron injections and magnetic field dipolarization in Mercury's magnetotail. Between March 2013 and April 2015, we identify 2,976 electron burst events within Mercury's magnetotail, 538 of which are closely associated with dipolarization events. These dipolarizations are detected on the basis of their rapid ( 2 s) increase in the northward component of the tail magnetic field (ΔBz 30 nT), which typically persists for 10 s. Similar to those at Earth, we find that these dipolarizations appear to be low-entropy, depleted flux tubes convecting planetward following the collapse of the inner magnetotail. We find that electrons experience brief, yet intense, betatron and Fermi acceleration during these dipolarizations, reaching energies 130 keV and contributing to nightside precipitation. Thermal protons experience only modest betatron acceleration. While only 25% of energetic electron events in Mercury's magnetotail are directly associated with dipolarization, the remaining events are consistent with the Near-Mercury Neutral Line model of magnetotail injection and eastward drift about Mercury, finding that electrons may participate in Shabansky-like closed drifts about the planet. Magnetotail dipolarization may be the dominant source of energetic electron acceleration in Mercury's magnetosphere.

Collective excitation frequencies and stationary states of trapped dipolar Bose-Einstein condensates in the Thomas-Fermi regime

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bijnen, R. M. W. van; Department of Physics and Astronomy, McMaster University, Hamilton, Ontario L8S 4M1; Parker, N. G.

We present a general method for obtaining the exact static solutions and collective excitation frequencies of a trapped Bose-Einstein condensate (BEC) with dipolar atomic interactions in the Thomas-Fermi regime. The method incorporates analytic expressions for the dipolar potential of an arbitrary polynomial density profile, thereby reducing the problem of handling nonlocal dipolar interactions to the solution of algebraic equations. We comprehensively map out the static solutions and excitation modes, including non-cylindrically-symmetric traps, and also the case of negative scattering length where dipolar interactions stabilize an otherwise unstable condensate. The dynamical stability of the excitation modes gives insight into the onsetmore » of collapse of a dipolar BEC. We find that global collapse is consistently mediated by an anisotropic quadrupolar collective mode, although there are two trapping regimes in which the BEC is stable against quadrupole fluctuations even as the ratio of the dipolar to s-wave interactions becomes infinite. Motivated by the possibility of a fragmented condensate in a dipolar Bose gas due to the partially attractive interactions, we pay special attention to the scissors modes, which can provide a signature of superfluidity, and identify a long-range restoring force which is peculiar to dipolar systems. As part of the supporting material for this paper we provide the computer program used to make the calculations, including a graphical user interface.« less

Overcoming limits to near-field radiative heat transfer in uniform planar media through multilayer optimization.

PubMed

Jin, Weiliang; Messina, Riccardo; Rodriguez, Alejandro W

2017-06-26

Radiative heat transfer between uniform plates is bounded by the narrow range and limited contribution of surface waves. Using a combination of analytical calculations and numerical gradient-based optimization, we show that such a limitation can be overcome in complicated multilayer geometries, allowing the scattering and coupling rates of slab resonances to be altered over a broad range of evanescent wavevectors. We conclude that while the radiative flux between two inhomogeneous slabs can only be weakly enhanced, the flux between a dipolar particle and an inhomogeneous slab-proportional to the local density of states-can be orders of magnitude larger, albeit at the expense of increased frequency selectivity. A brief discussion of hyperbolic metamaterials shows that they provide far less enhancement than optimized inhomogeneous slabs.

Matter-Wave Optics of Diatomic Molecules

DTIC Science & Technology

2012-10-23

81.013802 10/11/2012 32.00 Swati Singh , Pierre Meystre. Atomic probe Wigner tomography of a nanomechanical system, Physical Review A, (04 2010): 41804...PhysRevA.78.041801 10/11/2012 3.00 S. Singh , M. Bhattacharya, O. Dutta, P. Meystre. Coupling Nanomechanical Cantilevers to Dipolar Molecules...degenerate matter waves, Physical Review A, (02 2009): 0. doi: 10.1103/PhysRevA.79.023622 10/11/2012 10.00 M. Bhattacharya, S. Singh , P. -L. Giscard

Chiral magnetism of magnetic adatoms generated by Rashba electrons

NASA Astrophysics Data System (ADS)

Bouaziz, Juba; dos Santos Dias, Manuel; Ziane, Abdelhamid; Benakki, Mouloud; Blügel, Stefan; Lounis, Samir

2017-02-01

We investigate long-range chiral magnetic interactions among adatoms mediated by surface states spin-splitted by spin-orbit coupling. Using the Rashba model, the tensor of exchange interactions is extracted wherein a thepseudo-dipolar interaction is found, in addition to the usual isotropic exchange interaction and the Dzyaloshinskii-Moriya interaction. We find that, despite the latter interaction, collinear magnetic states can still be stabilized by the pseudo-dipolar interaction. The interadatom distance controls the strength of these terms, which we exploit to design chiral magnetism in Fe nanostructures deposited on a Au(111) surface. We demonstrate that these magnetic interactions are related to superpositions of the out-of-plane and in-plane components of the skyrmionic magnetic waves induced by the adatoms in the surrounding electron gas. We show that, even if the interatomic distance is large, the size and shape of the nanostructures dramatically impacts on the strength of the magnetic interactions, thereby affecting the magnetic ground state. We also derive an appealing connection between the isotropic exchange interaction and the Dzyaloshinskii-Moriya interaction, which relates the latter to the first-order change of the former with respect to spin-orbit coupling. This implies that the chirality defined by the direction of the Dzyaloshinskii-Moriya vector is driven by the variation of the isotropic exchange interaction due to the spin-orbit interaction.

Paramagnetic resonance studies of bistrispyrazolylborate cobalt(II) and related derivatives

NASA Astrophysics Data System (ADS)

Myers, William K.

Herein, a systematic frozen solution electron-nuclear double resonance (ENDOR) study of high-spin Co(II) complexes is reported to demonstrate the efficacy of methyl substitutions as a means of separating dipolar and contact coupling, and further, to increase the utility of high-spin Co(II) as a spectroscopic probe for the ubiquitous, but spectroscopically-silent Zn(II) metalloenzymes. High-spin (hs) Co(II) has been subject of paramagnetic resonance studies for over 50 years and has been used as a spectroscopic probe for Zn metalloenzymes for over 35 years. However, as will be seen, the inherent complexity of the electronic properties of the cobaltous ion remains to be exploited to offer a wealth of information on Zn(II) enzymatic environments. Specifically, ENDOR measurements on bistrispyrazolylborate cobalt(II) confirm the utility of the novel method of methyl substitution to differentiate dipolar and Fermi contact couplings. An extensive set of electron paramagnetic resonance (EPR) simulations were performed. Software was developed to implement an ENDOR control interface. Finally, proton relaxation measurements were made in the range of 12-42 MHz, which were accounted for with the large g-value anisotropy of the Co(II) compounds. Taken as a whole, these studies point to the rich complexity of the electronic structure of high-spin cobalt(II) and, when sufficiently well-characterized, the great utility it has as a surrogate of biological Zn(II).

NMR dipolar constants of motion in liquid crystals: Jeener-Broekaert, double quantum coherence experiments and numerical calculation on a 10-spin cluster.

PubMed

Segnorile, H H; Bonin, C J; González, C E; Acosta, R H; Zamar, R C

2009-10-01

Two proton quasi-equilibrium states were previously observed in nematic liquid crystals, namely the S and W quasi-invariants. Even though the experimental evidence suggested that they originate in a partition of the spin dipolar energy into a strong and a weak part, respectively, from a theoretical viewpoint, the existence of an appropriate energy scale which allows such energy separation remains to be confirmed and a representation of the quasi-invariants is still to be given. We compare the dipolar NMR signals yielded both by the Jeener-Broekaert (JB) experiment as a function of the preparation time and the free evolution of the double quantum coherence (DQC) spectra excited from the S state, with numerical calculations carried out from first principles under different models for the dipolar quasi-invariants, in a 10-spin cluster which represents the 5CB (4(')-pentyl-4-biphenyl-carbonitrile) molecule. The calculated signals qualitatively agree with the experiments and the DQC spectra as a function of the single-quantum detection time are sensible enough to the different models to allow both to probe the physical nature of the initial dipolar-ordered state and to assign a subset of dipolar interactions to each constant of motion, which are compatible with the experiments. As a criterion for selecting a suitable quasi-equilibrium model of the 5CB molecule, we impose on the time evolution operator consistency with the occurrence of two dipolar quasi-invariants, that is, the calculated spectra must be unaffected by truncation of non-secular terms of the weaker dipolar energy. We find that defining the S quasi-invariant as the subset of the dipolar interactions of each proton with its two nearest neighbours yields a realistic characterization of the dipolar constants of motion in 5CB. We conclude that the proton-spin system of the 5CB molecule admits a partition of the dipolar energy into a bilinear strong and a multiple-spin weak contributions therefore providing two orthogonal constants of motion, which can be prepared and observed by means of the JB experiment. This feature, which implies the existence of two timescales of very different nature in the proton-spin dynamics, is ultimately dictated by the topology of the spin distribution in the dipole network and can be expected in other liquid crystals. Knowledge of the nature of the dipolar quasi-invariants will be useful in studies of dipolar-order relaxation, decoherence and multiple quantum NMR experiments where the initial state is a dipolar-ordered one.

Catalysis of a 1,3-dipolar reaction by distorted DNA incorporating a heterobimetallic platinum(ii) and copper(ii) complex.

PubMed

Rivilla, Iván; de Cózar, Abel; Schäfer, Thomas; Hernandez, Frank J; Bittner, Alexander M; Eleta-Lopez, Aitziber; Aboudzadeh, Ali; Santos, José I; Miranda, José I; Cossío, Fernando P

2017-10-01

A novel catalytic system based on covalently modified DNA is described. This catalyst promotes 1,3-dipolar reactions between azomethine ylides and maleimides. The catalytic system is based on the distortion of the double helix of DNA by means of the formation of Pt(ii) adducts with guanine units. This distortion, similar to that generated in the interaction of DNA with platinum chemotherapeutic drugs, generates active sites that can accommodate N -metallated azomethine ylides. The proposed reaction mechanism, based on QM(DFT)/MM calculations, is compatible with thermally allowed concerted (but asynchronous) [π4s + π2s] mechanisms leading to the exclusive formation of racemic endo -cycloadducts.

Thermodynamics of ferrofluids in applied magnetic fields.

PubMed

Elfimova, Ekaterina A; Ivanov, Alexey O; Camp, Philip J

2013-10-01

The thermodynamic properties of ferrofluids in applied magnetic fields are examined using theory and computer simulation. The dipolar hard sphere model is used. The second and third virial coefficients (B(2) and B(3)) are evaluated as functions of the dipolar coupling constant λ, and the Langevin parameter α. The formula for B(3) for a system in an applied field is different from that in the zero-field case, and a derivation is presented. The formulas are compared to results from Mayer-sampling calculations, and the trends with increasing λ and α are examined. Very good agreement between theory and computation is demonstrated for the realistic values λ≤2. The analytical formulas for the virial coefficients are incorporated in to various forms of virial expansion, designed to minimize the effects of truncation. The theoretical results for the equation of state are compared against results from Monte Carlo simulations. In all cases, the so-called logarithmic free energy theory is seen to be superior. In this theory, the virial expansion of the Helmholtz free energy is re-summed in to a logarithmic function. Its success is due to the approximate representation of high-order terms in the virial expansion, while retaining the exact low-concentration behavior. The theory also yields the magnetization, and a comparison with simulation results and a competing modified mean-field theory shows excellent agreement. Finally, the putative field-dependent critical parameters for the condensation transition are obtained and compared against existing simulation results for the Stockmayer fluid. Dipolar hard spheres do not undergo the transition, but the presence of isotropic attractions, as in the Stockmayer fluid, gives rise to condensation even in zero field. A comparison of the relative changes in critical parameters with increasing field strength shows excellent agreement between theory and simulation, showing that the theoretical treatment of the dipolar interactions is robust.

Novel phase transitions in coupled dipolar chains.

NASA Astrophysics Data System (ADS)

Mellado, Paula

We study the properties of a classical magnetic system realized by two chains of U(1) rotors coupled via Coulomb interactions in the dumbbell approach. Magnets in chain I and chain II rotate in the x-z and y-z planes respectively. Ground state correlations and the system wave excitation spectrum are found using spin wave theory. The displacement ''d'' of chain II from chain I induces dynamics in the system and yields two first order magnetic phase transitions. The transitions happen at critical displacements, which notably, are independent of the magnetic charge at the tips of the magnets, suggesting a geometrical origin. This work was supported by Fondecyt under Grant No. 1160239.

Phase behavior of a simple dipolar fluid under shear flow in an electric field.

PubMed

McWhirter, J Liam

2008-01-21

Nonequilibrium molecular dynamics simulations are performed on a dense simple dipolar fluid under a planar Couette shear flow. Shear generates heat, which is removed by thermostatting terms added to the equations of motion of the fluid particles. The spatial structure of simple fluids at high shear rates is known to depend strongly on the thermostatting mechanism chosen. Kinetic thermostats are either biased or unbiased: biased thermostats neglect the existence of secondary flows that appear at high shear rates superimposed upon the linear velocity profile of the fluid. Simulations that employ a biased thermostat produce a string phase where particles align in strings with hexagonal symmetry along the direction of the flow. This phase is known to be a simulation artifact of biased thermostatting, and has not been observed by experiments on colloidal suspensions under shear flow. In this paper, we investigate the possibility of using a suitably directed electric field, which is coupled to the dipole moments of the fluid particles, to stabilize the string phase. We explore several thermostatting mechanisms where either the kinetic or configurational fluid degrees of freedom are thermostated. Some of these mechanisms do not yield a string phase, but rather a shear-thickening phase; in this case, we find the influence of the dipolar interactions and external field on the packing structure, and in turn their influence on the shear viscosity at the onset of this shear-thickening regime.

Effect of simple solutes on the long range dipolar correlations in liquid water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baul, Upayan, E-mail: upayanb@imsc.res.in; Anishetty, Ramesh, E-mail: ramesha@imsc.res.in; Vemparala, Satyavani, E-mail: vani@imsc.res.in

2016-03-14

Intermolecular correlations in liquid water at ambient conditions have generally been characterized through short range density fluctuations described through the atomic pair distribution functions. Recent numerical and experimental results have suggested that such a description of order or structure in liquid water is incomplete and there exist considerably longer ranged orientational correlations in water that can be studied through dipolar correlations. In this study, using large scale classical, atomistic molecular dynamics simulations using TIP4P-Ew and TIP3P models of water, we show that salts such as sodium chloride (NaCl), potassium chloride (KCl), caesium chloride (CsCl), and magnesium chloride (MgCl{sub 2}) havemore » a long range effect on the dipolar correlations, which cannot be explained by the notion of structure making and breaking by dissolved ions. Observed effects are explained through orientational stratification of water molecules around ions and their long range coupling to the global hydrogen bond network by virtue of the sum rule for water. The observations for single hydrophilic solutes are contrasted with the same for a single methane (CH{sub 4}) molecule. We observe that even a single small hydrophobe can result in enhancement of long range orientational correlations in liquid water, contrary to the case of dissolved ions, which have been observed to have a reducing effect. The observations from this study are discussed in the context of hydrophobic effect.« less

Confocal shift interferometry of coherent emission from trapped dipolar excitons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Repp, J.; Nanosystems Initiative Munich; Center for NanoScience and Fakultät für Physik, Ludwig-Maximilians-Universität, Geschwister-Scholl-Platz 1, 80539 München

2014-12-15

We introduce a confocal shift-interferometer based on optical fibers. The presented spectroscopy allows measuring coherence maps of luminescent samples with a high spatial resolution even at cryogenic temperatures. We apply the spectroscopy onto electrostatically trapped, dipolar excitons in a semiconductor double quantum well. We find that the measured spatial coherence length of the excitonic emission coincides with the point spread function of the confocal setup. The results are consistent with a temporal coherence of the excitonic emission down to temperatures of 250 mK.

Quantum Fluctuations in Quasi-One-Dimensional Dipolar Bose-Einstein Condensates

NASA Astrophysics Data System (ADS)

Edler, D.; Mishra, C.; Wächtler, F.; Nath, R.; Sinha, S.; Santos, L.

2017-08-01

Recent experiments have revealed that beyond-mean-field corrections are much more relevant in weakly interacting dipolar condensates than in their nondipolar counterparts. We show that in quasi-one-dimensional geometries quantum corrections in dipolar and nondipolar condensates are strikingly different due to the peculiar momentum dependence of the dipolar interactions. The energy correction of the condensate presents not only a modified density dependence, but it may even change from attractive to repulsive at a critical density due to the surprising role played by the transversal directions. The anomalous quantum correction translates into a strongly modified physics for quantum-stabilized droplets and dipolar solitons. Moreover, and for similar reasons, quantum corrections of three-body correlations, and hence of three-body losses, are strongly modified by the dipolar interactions. This intriguing physics can be readily probed in current experiments with magnetic atoms.

Quantum Fluctuations in Quasi-One-Dimensional Dipolar Bose-Einstein Condensates.

PubMed

Edler, D; Mishra, C; Wächtler, F; Nath, R; Sinha, S; Santos, L

2017-08-04

Recent experiments have revealed that beyond-mean-field corrections are much more relevant in weakly interacting dipolar condensates than in their nondipolar counterparts. We show that in quasi-one-dimensional geometries quantum corrections in dipolar and nondipolar condensates are strikingly different due to the peculiar momentum dependence of the dipolar interactions. The energy correction of the condensate presents not only a modified density dependence, but it may even change from attractive to repulsive at a critical density due to the surprising role played by the transversal directions. The anomalous quantum correction translates into a strongly modified physics for quantum-stabilized droplets and dipolar solitons. Moreover, and for similar reasons, quantum corrections of three-body correlations, and hence of three-body losses, are strongly modified by the dipolar interactions. This intriguing physics can be readily probed in current experiments with magnetic atoms.

Energetic electron injections and dipolarization events in Mercury's magnetotail: Substorm dynamics

NASA Astrophysics Data System (ADS)

Dewey, R. M.; Slavin, J. A.; Raines, J. M.; Imber, S.; Baker, D. N.; Lawrence, D. J.

2017-12-01

Despite its small size, Mercury's terrestrial-like magnetosphere experiences brief, yet intense, substorm intervals characterized by features similar to at Earth: loading/unloading of the tail lobes with open magnetic flux, dipolarization of the magnetic field at the inner edge of the plasma sheet, and, the focus of this presentation, energetic electron injection. We use the Gamma-Ray Spectrometer's high-time resolution (10 ms) energetic electron measurements to determine the relationship between substorm activity and energetic electron injections coincident with dipolarization fronts in the magnetotail. These dipolarizations were detected on the basis of their rapid ( 2 s) increase in the northward component of the tail magnetic field (ΔBz 30 nT), which typically persists for 10 s. We estimate the typical flow channel to be 0.15 RM, planetary convection speed of 750 km/s, cross-tail potential drop of 7 kV, and flux transport of 0.08 MWb for each dipolarization event, suggesting multiple simultaneous and sequential dipolarizations are required to unload the >1 MWb of magnetic flux typically returned to the dayside magnetosphere during a substorm interval. Indeed, while we observe most dipolarization-injections to be isolated or in small chains of events (i.e., 1-3 events), intervals of sawtooth-like injections with >20 sequential events are also present. The typical separation between dipolarization-injection events is 10 s. Magnetotail dipolarization, in addition to being a powerful source of electron acceleration, also plays a significant role in the substorm process at Mercury.

Electron heating and Tp/Te variations during magnetic dipolarizations

NASA Astrophysics Data System (ADS)

Grigorenko, Elena; Kronberg, Elena; Daly, Patrick; Ganushkina, Natalia; Lavraud, Benoit; Sauvaud, Jean-Andre; Zelenyi, Lev

2017-04-01

The proton-to-electron temperature ratio (Tp/Te) in the plasma sheet (PS) of the Earth's magnetotail is studied by using 5 years of Cluster observations (2001-2005). The PS intervals are searched within a region defined with -19

Bose-Einstein condensation and superfluidity of dipolar excitons in a phosphorene double layer

NASA Astrophysics Data System (ADS)

Berman, Oleg L.; Gumbs, Godfrey; Kezerashvili, Roman Ya.

2017-07-01

We study the formation of dipolar excitons and their superfluidity in a phosphorene double layer. The analytical expressions for the single dipolar exciton energy spectrum and wave function are obtained. It is predicted that a weakly interacting gas of dipolar excitons in a double layer of black phosphorus exhibits superfluidity due to the dipole-dipole repulsion between the dipolar excitons. In calculations are employed the Keldysh and Coulomb potentials for the interaction between the charge carriers to analyze the influence of the screening effects on the studied phenomena. It is shown that the critical velocity of superfluidity, the spectrum of collective excitations, concentrations of the superfluid and normal component, and mean-field critical temperature for superfluidity are anisotropic and demonstrate the dependence on the direction of motion of dipolar excitons. The critical temperature for superfluidity increases if the exciton concentration and the interlayer separation increase. It is shown that the dipolar exciton binding energy and mean-field critical temperature for superfluidity are sensitive to the electron and hole effective masses. The proposed experiment to observe a directional superfluidity of excitons is addressed.

Radiation Database for Earth and Mars Entry

DTIC Science & Technology

2008-11-17

SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT SAR 18 . NUMBER OF PAGES 40 19a. NAME OF RESPONSIBLE PERSON a. REPORT unclassified b...ABSTRACT unclassified c. THIS PAGE unclassified Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std Z39- 18 wall, and zero otherwise. The radiative...coupling scheme, we have the additional selection rules for the electric dipolar transition ∆S = 0, (16) ∆L = 0,±1, (17) L = 0 6↔ L = 0 ( 18 ) where we have

Asymmetric dipolar ring

DOEpatents

Prosandeev, Sergey A.; Ponomareva, Inna V.; Kornev, Igor A.; Bellaiche, Laurent M.

2010-11-16

A device having a dipolar ring surrounding an interior region that is disposed asymmetrically on the ring. The dipolar ring generates a toroidal moment switchable between at least two stable states by a homogeneous field applied to the dipolar ring in the plane of the ring. The ring may be made of ferroelectric or magnetic material. In the former case, the homogeneous field is an electric field and in the latter case, the homogeneous field is a magnetic field.

3D Double-Quantum/Double-Quantum Exchange Spectroscopy of Protons under 100 kHz Magic Angle Spinning.

PubMed

Zhang, Rongchun; Duong, Nghia Tuan; Nishiyama, Yusuke; Ramamoorthy, Ayyalusamy

2017-06-22

Solid-state 1 H NMR spectroscopy has attracted much attention in the recent years due to the remarkable spectral resolution improvement by ultrafast magic-angle-spinning (MAS) as well as due to the sensitivity enhancement rendered by proton detection. Although these developments have enabled the investigation of a variety of challenging chemical and biological solids, the proton spectral resolution is still poor for many rigid solid systems owing to the presence of conformational heterogeneity and the unsuppressed residual proton-proton dipolar couplings even with the use of the highest currently feasible sample spinning speed of ∼130 kHz. Although a further increase in the spinning speed of the sample could be beneficial to some extent, there is a need for alternate approaches to enhance the spectral resolution. Herein, by fully utilizing the benefits of double-quantum (DQ) coherences, we propose a single radio frequency channel proton-based 3D pulse sequence that correlates double-quantum (DQ), DQ, and single-quantum (SQ) chemical shifts of protons. In addition to the two-spin homonuclear proximity information, the proposed 3D DQ/DQ/SQ experiment also enables the extraction of three-spin and four-spin proximities, which could be beneficial for revealing the dipolar coupled proton network in the solid state. Besides, the 2D DQ/DQ spectrum sliced at different isotropic SQ chemical shift values of the 3D DQ/DQ/SQ spectrum will also facilitate the identification of DQ correlation peaks and improve the spectral resolution, as it only provides the local homonuclear correlation information associated with the specific protons selected by the SQ chemical shift frequency. The 3D pulse sequence and its efficiency are demonstrated experimentally on small molecular compounds in the solid state. We expect that this approach would create avenues for further developments by suitably combining the benefits of partial deuteration of samples, selective excitation/decoupling pulses, heteronuclear spins for spectral editing, and nonuniform sampling.

Self-assembling hybrid diamond-biological quantum devices

NASA Astrophysics Data System (ADS)

Albrecht, A.; Koplovitz, G.; Retzker, A.; Jelezko, F.; Yochelis, S.; Porath, D.; Nevo, Y.; Shoseyov, O.; Paltiel, Y.; Plenio, M. B.

2014-09-01

The realization of scalable arrangements of nitrogen vacancy (NV) centers in diamond remains a key challenge on the way towards efficient quantum information processing, quantum simulation and quantum sensing applications. Although technologies based on implanting NV-centers in bulk diamond crystals or hybrid device approaches have been developed, they are limited by the achievable spatial resolution and by the intricate technological complexities involved in achieving scalability. We propose and demonstrate a novel approach for creating an arrangement of NV-centers, based on the self-assembling capabilities of biological systems and their beneficial nanometer spatial resolution. Here, a self-assembled protein structure serves as a structural scaffold for surface functionalized nanodiamonds, in this way allowing for the controlled creation of NV-structures on the nanoscale and providing a new avenue towards bridging the bio-nano interface. One-, two- as well as three-dimensional structures are within the scope of biological structural assembling techniques. We realized experimentally the formation of regular structures by interconnecting nanodiamonds using biological protein scaffolds. Based on the achievable NV-center distances of 11 nm, we evaluate the expected dipolar coupling interaction with neighboring NV-centers as well as the expected decoherence time. Moreover, by exploiting these couplings, we provide a detailed theoretical analysis on the viability of multiqubit quantum operations, suggest the possibility of individual addressing based on the random distribution of the NV intrinsic symmetry axes and address the challenges posed by decoherence and imperfect couplings. We then demonstrate in the last part that our scheme allows for the high-fidelity creation of entanglement, cluster states and quantum simulation applications.

Loschmidt echo as a robust decoherence quantifier for many-body systems

NASA Astrophysics Data System (ADS)

Zangara, Pablo R.; Dente, Axel D.; Levstein, Patricia R.; Pastawski, Horacio M.

2012-07-01

We employ the Loschmidt echo, i.e., the signal recovered after the reversal of an evolution, to identify and quantify the processes contributing to decoherence. This procedure, which has been extensively used in single-particle physics, is employed here in a spin ladder. The isolated chains have 1/2 spins with XY interaction and their excitations would sustain a one-body-like propagation. One of them constitutes the controlled system S whose reversible dynamics is degraded by the weak coupling with the uncontrolled second chain, i.e., the environment E. The perturbative SE coupling is swept through arbitrary combinations of XY and Ising-like interactions, that contain the standard Heisenberg and dipolar ones. Different time regimes are identified for the Loschmidt echo dynamics in this perturbative configuration. In particular, the exponential decay scales as a Fermi golden rule, where the contributions of the different SE terms are individually evaluated and analyzed. Comparisons with previous analytical and numerical evaluations of decoherence based on the attenuation of specific interferences show that the Loschmidt echo is an advantageous decoherence quantifier at any time, regardless of the S internal dynamics.

Rotation Dynamics Do Not Determine the Unexpected Isotropy of Methyl Radical EPR Spectra.

PubMed

Benetis, Nikolas P; Dmitriev, Yurij; Mocci, Francesca; Laaksonen, Aatto

2015-09-03

A simple first-principles electronic structure computation, further qc (quantum chemistry) computation, of the methyl radical gives three equal hf (hyperfine) couplings for the three protons with the unpaired electron. The corresponding dipolar tensors were notably rhombic and had different orientations and regular magnitude components, as they should, but what the overall A-tensor was seen by the electron spin is a different story! The final g = (2.002993, 2.002993, 2.002231) tensor and the hf coupling results obtained in vacuum, at the B3LYP/EPRIII level of theory clearly indicate that in particular the above A = (-65.19, -65.19, 62.54) MHz tensor was axial to a first approximation without considering any rotational dynamics for the CH3. This approximation was not applicable, however, for the trifluoromethyl CF3 radical, a heavier and nonplanar rotor with very anisotropic hf coupling, used here for comparison. Finally, a derivation is presented explaining why there is actually no need for the CH3 radicals to consider additional rotational dynamics in order for the electron to obtain an axially symmetric hf (hyperfine) tensor by considering the simultaneous dipolar couplings of the three protons. An additional consequence is an almost isotropic A-tensor for the electron spin of the CH3 radical. To the best of our knowledge, this point has not been discussed in the literature before. The unexpected isotropy of the EPR parameters of CH3 was solely attributed to the rotational dynamics and was not clearly separated from the overall symmetry of the species. The present theoretical results allowed a first explanation of the "forbidden" satellite lines in the CH3 EPR spectrum. The satellites are a fingerprint of the radical rotation, helping thus in distinguishing the CH3 reorientation from quantum rotation at very low temperatures.

Computing distance distributions from dipolar evolution data with overtones: RIDME spectroscopy with Gd(iii)-based spin labels.

PubMed

Keller, Katharina; Mertens, Valerie; Qi, Mian; Nalepa, Anna I; Godt, Adelheid; Savitsky, Anton; Jeschke, Gunnar; Yulikov, Maxim

2017-07-21

Extraction of distance distributions between high-spin paramagnetic centers from relaxation induced dipolar modulation enhancement (RIDME) data is affected by the presence of overtones of dipolar frequencies. As previously proposed, we account for these overtones by using a modified kernel function in Tikhonov regularization analysis. This paper analyzes the performance of such an approach on a series of model compounds with the Gd(iii)-PyMTA complex serving as paramagnetic high-spin label. We describe the calibration of the overtone coefficients for the RIDME kernel, demonstrate the accuracy of distance distributions obtained with this approach, and show that for our series of Gd-rulers RIDME technique provides more accurate distance distributions than Gd(iii)-Gd(iii) double electron-electron resonance (DEER). The analysis of RIDME data including harmonic overtones can be performed using the MATLAB-based program OvertoneAnalysis, which is available as open-source software from the web page of ETH Zurich. This approach opens a perspective for the routine use of the RIDME technique with high-spin labels in structural biology and structural studies of other soft matter.

Frustrated Magnetism of Dipolar Molecules on a Square Optical Lattice: Prediction of a Quantum Paramagnetic Ground State

NASA Astrophysics Data System (ADS)

Zou, Haiyuan; Zhao, Erhai; Liu, W. Vincent

2017-08-01

Motivated by the experimental realization of quantum spin models of polar molecule KRb in optical lattices, we analyze the spin 1 /2 dipolar Heisenberg model with competing anisotropic, long-range exchange interactions. We show that, by tilting the orientation of dipoles using an external electric field, the dipolar spin system on square lattice comes close to a maximally frustrated region similar, but not identical, to that of the J1-J2 model. This provides a simple yet powerful route to potentially realize a quantum spin liquid without the need for a triangular or kagome lattice. The ground state phase diagrams obtained from Schwinger-boson and spin-wave theories consistently show a spin disordered region between the Néel, stripe, and spiral phase. The existence of a finite quantum paramagnetic region is further confirmed by an unbiased variational ansatz based on tensor network states and a tensor renormalization group.

Quantum-Fluctuation-Driven Crossover from a Dilute Bose-Einstein Condensate to a Macrodroplet in a Dipolar Quantum Fluid

NASA Astrophysics Data System (ADS)

Chomaz, L.; Baier, S.; Petter, D.; Mark, M. J.; Wächtler, F.; Santos, L.; Ferlaino, F.

2016-10-01

In a joint experimental and theoretical effort, we report on the formation of a macrodroplet state in an ultracold bosonic gas of erbium atoms with strong dipolar interactions. By precise tuning of the s -wave scattering length below the so-called dipolar length, we observe a smooth crossover of the ground state from a dilute Bose-Einstein condensate to a dense macrodroplet state of more than 2 ×104 atoms . Based on the study of collective excitations and loss features, we prove that quantum fluctuations stabilize the ultracold gas far beyond the instability threshold imposed by mean-field interactions. Finally, we perform expansion measurements, showing that although self-bound solutions are prevented by losses, the interplay between quantum stabilization and losses results in a minimal time-of-flight expansion velocity at a finite scattering length.

A test of the significance of intermolecular vibrational coupling in isotopic fractionation

DOE PAGES

Herman, Michael F.; Currier, Robert P.; Peery, Travis B.; ...

2017-07-15

Intermolecular coupling of dipole moments is studied for a model system consisting of two diatomic molecules (AB monomers) arranged co-linearly and which can form non-covalently bound dimers. The dipolar coupling is a function of the bond length in each molecule as well as of the distance between the centers-of-mass of the two molecules. The calculations show that intermolecular coupling of the vibrations results in an isotope-dependent modification of the AB-AB intermolecular potential. This in turn alters the energies of the low-lying bound states of the dimers, producing isotope-dependent changes in the AB-AB dimer partition function. Explicit inclusion of intermolecular vibrationalmore » coupling then changes the predicted gas-dimer isotopic fractionation. In addition, a mass dependence in the intermolecular potential can also result in changes in the number of bound dimer states in an equilibrium mixture. This in turn leads to a significant dimer population shift in the model monomer-dimer equilibrium system considered here. Finally, the results suggest that intermolecular coupling terms should be considered when probing the origins of isotopic fractionation.« less

When Ethyl Isocyanoacetate Meets Isatins: A 1,3-Dipolar/Inverse 1,3-Dipolar/Olefination Reaction for Access to 3-Ylideneoxindoles.

PubMed

Yuan, Wen-Kui; Cui, Tao; Liu, Wei; Wen, Li-Rong; Li, Ming

2018-03-16

A new CuI/1,10-phen-catalyzed reaction for the synthesis of 3-ylideneoxindoles from readily available isatins and ethyl isocyanoacetate, in which ethyl isocyanoacetate acts as a latent two-carbon donor like the Wittig reagent, is reported. A tandem procedure including 1,3-dipolar cycloaddition/inverse 1,3-dipolar ring opening/olefination allows the preparation of 3-ylideneoxindoles with broad functional group tolerance.

The Relationship Between Dipolarization Fronts and Pi2 Pulsations in the Near-Earth Magnetotail - A MHD Case Study

NASA Astrophysics Data System (ADS)

Ream, J. B.; Walker, R. J.; Ashour-Abdalla, M.; El-Alaoui, M.

2011-12-01

We performed a global MHD simulation of a substorm event on 14 September 2004 in order to investigate the link between Pi2 generation and dipolarization fronts. Pi2 pulsations (T = 40-150 s) measured by ground-based instruments are typically used as an indicator of substorm onset, therefore, understanding how and where they are generated is vital to understanding the series of events leading up to onset. Kepko et al. [1999] suggested that the compression regions and velocity variations associated with earthward propagating dipolarization fronts directly drive Pi2 pulsations. Similarly, Panov et al. [2011] suggested that Pi2 pulsations are generated by the overshoot and rebound of bursty bulk flows. Dipolarization fronts are step-wise enhancements in Bz which are associated with fast (>100km/s) earthward flows and are followed by tailward expansion due to pile-up at the high pressure region where the magnetic field lines transition from a stretched to a dipolar configuration. Cao et al. [2009] have presented observations from Double Star (TC1), Cluster 4 and Polar of a substorm with onset at 18:22 UT. During this event a dipolarization front was observed by Double Star at ~18:25, and dipolarization associated expansion was observed by Cluster 4 at ~18:50 and Polar at ~18:55 UT. The spacecraft were positioned at (-10.2, -1.6, 1.2), (-16.4, 1.6, 2.2) and (-7.5, -1.8, -4.9) RE in GSM coordinates respectively. The simulation was carried out with the UCLA global MHD code [El-Alaoui (2001), Raeder (1998)], using Geotail, located near the bow shock at ~24 RE, as the solar wind monitor. The solar wind magnetic field data were rotated into a minimum variance frame to be used as input for the simulation. The results from the simulation have been compared to observations and do a good job reproducing the structures observed by all three satellites. Around the time of onset, we have identified a dipolarization front near midnight which originates at ~12 RE. We show that as the dipolarization front begins to travel earthward, Pi2 fluctuations are generated in the pressure and velocity components which propagate along the plasma sheet into the inner magnetosphere. Inside ~-7 RE the frequency seen in the velocity perturbations is matched by perturbations in pressure and magnetic field components. References Ashour-Abdalla, M., et al (2011), Observations and simulations of non-local acceleration of electrons in magnetotail magnetic reconnection events, Nature Physics, vol.7. Cao, X., et al. (2008), Multispacecraft and ground-based observations of substorm timing and activations: Two case studies, J. Geophys. Res., 113, A07S25. El-Alaoui, M. (2001), Current disruption during November 24, 1996 substorm, J. Geophys. Res., 106, 6229- 6245. Kepko, L. and M. Kivelson (1999) Generation of Pi2 pulsations by bursty bulk flows, J. Geophys Res. 104(A11),25,021-25,034. Panov, E. V., et al (2010), Multiple overshoot and rebound of a bursty bulk flow, Geophys. Res. Lett., 37, L08103. Raeder, J., et al. (1998), The Geospace Environment Modeling Grand Challenge: Results from a global geospace circulation model, J. Geophys. Res., 103, 14,787.

Acceleration and Precipitation of Electrons during Substorm Dipolarization Events

NASA Astrophysics Data System (ADS)

Ashour-Abdalla, Maha; Richard, Robert; Donovan, Eric; Zhou, Meng; Goldstein, Mevlyn; El-Alaoui, Mostafa; Schriver, David; Walker, Raymond

Observations and modeling have established that during geomagnetically disturbed times the Earth’s magnetotail goes through large scale changes that result in enhanced electron precipitation into the ionosphere and earthward propagating dipolarization fronts that contain highly energized plasma. Such events originate near reconnection regions in the magnetotail at about 20-30 R_E down tail. As the dipolarization fronts propagate earthward, strong acceleration of both ions and electrons occurs due to a combination of non-adiabatic and adiabatic (betatron and Fermi) acceleration, with particle energies reaching up to 100 keV within the dipolarization front. One consequence of the plasma transport that occurs during these events is direct electron precipitation into the ionosphere, which form auroral precipitation. Using global kinetic simulations along with spacecraft and ground-based data, causes of electron precipitation are determined during well-documented, disturbed events. It is found that precipitation of keV electrons in the pre-midnight sector at latitudes around 70(°) occur due to two distinct physical processes: (1) higher latitude (≥72(°) ) precipitation due to electrons that undergo relatively rapid non-adiabatic pitch angle scattering into the loss cone just earthward of the reconnection region at around 20 R_E downtail, and (2) lower latitude (≤72(°) ) precipitation due to electrons that are more gradually accelerated primarily parallel to the geomagnetic field during its bounce motion by Fermi acceleration and enter the loss cone much closer to the Earth at 10-15 R_E, somewhat tailward of the dipolarization front. As the dipolarization fronts propagate earthward, the electron precipitation shifts to lower latitudes and occurs over a wider region in the auroral ionosphere. Our results show a direct connection between electron acceleration in the magnetotail and electron precipitation in the ionosphere during disturbed times. The electron precipitation due to the combination of these two mechanisms coincides spatially with observed auroral brightening during the disturbed event.

Conformation of flexibly linked triterpene dimers by using RDC-enhanced NMR spectroscopy

NASA Astrophysics Data System (ADS)

Lakshmi, Jerripothula K.; Pattnaik, Banita; Kavitha, Rachineni; Mallavadhani, Uppuluri V.; Jagadeesh, Bharatam

2018-06-01

Dimers of flexibly linked pentacyclic triterpene ursolic acid (UA) and its related frameworks such as asiatic acid (AA) and oleanolic acid (OA) have recently attracted significant attention due to their enhanced anti-cancer and anti-HCV activity compared to their respective monomers. Determination of conformation/inter-monomer orientation of these molecules is very important to understand their structure-activity relationship and to develop new scaffolds, which, however, is difficult through conventional NOE based solution-state NMR spectroscopy, due to lack of long-range NOEs. In the present work, we report a precise determination of conformation of two 1,2,3-triazole-linked triterpene dimer molecules, UA-AA and UA-OA, by employing one-bond Csbnd H residual dipolar couplings (RDCs) as additional long-range orientational restraints, measured in anisotropic PDMS/CDCl3 solvent medium.

Combining multinuclear high-resolution solid-state MAS NMR and computational methods for resonance assignment of glutathione tripeptide.

PubMed

Sardo, Mariana; Siegel, Renée; Santos, Sérgio M; Rocha, João; Gomes, José R B; Mafra, Luis

2012-06-28

We present a complete set of experimental approaches for the NMR assignment of powdered tripeptide glutathione at natural isotopic abundance, based on J-coupling and dipolar NMR techniques combined with (1)H CRAMPS decoupling. To fully assign the spectra, two-dimensional (2D) high-resolution methods, such as (1)H-(13)C INEPT-HSQC/PRESTO heteronuclear correlations (HETCOR), (1)H-(1)H double-quantum (DQ), and (1)H-(14)N D-HMQC correlation experiments, have been used. To support the interpretation of the experimental data, periodic density functional theory calculations together with the GIPAW approach have been used to calculate the (1)H and (13)C chemical shifts. It is found that the shifts calculated with two popular plane wave codes (CASTEP and Quantum ESPRESSO) are in excellent agreement with the experimental results.

Avoiding bias effects in NMR experiments for heteronuclear dipole-dipole coupling determinations: principles and application to organic semiconductor materials.

PubMed

Kurz, Ricardo; Cobo, Marcio Fernando; de Azevedo, Eduardo Ribeiro; Sommer, Michael; Wicklein, André; Thelakkat, Mukundan; Hempel, Günter; Saalwächter, Kay

2013-09-16

Carbon-proton dipole-dipole couplings between bonded atoms represent a popular probe of molecular dynamics in soft materials or biomolecules. Their site-resolved determination, for example, by using the popular DIPSHIFT experiment, can be challenged by spectral overlap with nonbonded carbon atoms. The problem can be solved by using very short cross-polarization (CP) contact times, however, the measured modulation curves then deviate strongly from the theoretically predicted shape, which is caused by the dependence of the CP efficiency on the orientation of the CH vector, leading to an anisotropic magnetization distribution even for isotropic samples. Herein, we present a detailed demonstration and explanation of this problem, as well as providing a solution. We combine DIPSHIFT experiments with the rotor-directed exchange of orientations (RODEO) method, and modifications of it, to redistribute the magnetization and obtain undistorted modulation curves. Our strategy is general in that it can also be applied to other types of experiments for heteronuclear dipole-dipole coupling determinations that rely on dipolar polarization transfer. It is demonstrated with perylene-bisimide-based organic semiconductor materials, as an example, in which measurements of dynamic order parameters reveal correlations of the molecular dynamics with the phase structure and functional properties. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct Observation of Optical Field Phase Carving in the Vicinity of Plasmonic Metasurfaces.

PubMed

Dagens, B; Février, M; Gogol, P; Blaize, S; Apuzzo, A; Magno, G; Mégy, R; Lerondel, G

2016-07-13

Plasmonic surfaces are mainly used for their optical intensity concentration properties that allow for enhancement of physical interaction like in nonlinear optics, optical sensors, or tweezers. Phase response in plasmonic resonances can also play a major role, especially in a periodic assembly of plasmonic resonators like metasurfaces. Here we show that localized surface plasmons collectively excited by a guided mode in a metallic nanostructure periodic chain present nonmonotonous phase variation along the 1D metasurface, resulting from both selective Bloch mode coupling and dipolar coupling. As shown by near-field measurements, the phase profile of the highly concentrated optical field is carved out in the vicinity of the metallic metasurface, paving the way to unusual local optical functions.

Artificial Dipolar Molecular Rotors

NASA Astrophysics Data System (ADS)

Horansky, R. D.; Magnera, T. F.; Price, J. C.; Michl, J.

Rotors are present in almost every macroscopic machine, converting rotational motion into energy of other forms, or converting other forms of energy into rotation. Rotation may be transmitted via belts or gears, converted into linear motion by various linkages, or used to drive propellers to produce fluid motion. Examples of macroscopic rotors include engines which couple to combustible energy sources, windmills which couple to air flows, and most generators of electricity. A key feature of these objects is the presence of a part with rotational freedom relative to a stationary frame. In this chapter we discuss the miniaturization of rotary machines all the way to the molecular scale, where chemical groups form the rotary and stationary parts. For a recent review of molecules with rotary and stationary parts see [1].

Covalent Coupling of Nanoparticles with Low-Density Functional Ligands to Surfaces via Click Chemistry

PubMed Central

Rianasari, Ina; de Jong, Michel P.; Huskens, Jurriaan; van der Wiel, Wilfred G.

2013-01-01

We demonstrate the application of the 1,3-dipolar cycloaddition (“click” reaction) to couple gold nanoparticles (Au NPs) functionalized with low densities of functional ligands. The ligand coverage on the citrate-stabilized Au NPs was adjusted by the ligand:Au surface atom ratio, while maintaining the colloidal stability of the Au NPs in aqueous solution. A procedure was developed to determine the driving forces governing the selectivity and reactivity of citrate-stabilized and ligand-functionalized Au NPs on patterned self-assembled monolayers. We observed selective and remarkably stable chemical bonding of the Au NPs to the complimentarily functionalized substrate areas, even when estimating that only 1–2 chemical bonds are formed between the particles and the substrate. PMID:23434666

Suppression of quantum phase interference in the molecular magnet Fe8 with dipolar-dipolar interaction

NASA Astrophysics Data System (ADS)

Chen, Zhi-De; Liang, J.-Q.; Shen, Shun-Qing

2002-09-01

Renormalized tunnel splitting with a finite distribution in the biaxial spin model for molecular magnets is obtained by taking into account the dipolar interaction of enviromental spins. Oscillation of the resonant tunnel splitting with a transverse magnetic field along the hard axis is smeared by the finite distribution, which subsequently affects the quantum steps of the hysteresis curve evaluated in terms of the modified Landau-Zener model of spin flipping induced by the sweeping field. We conclude that the dipolar-dipolar interaction drives decoherence of quantum tunneling in the molecular magnet Fe8, which explains why the quenching points of tunnel splitting between odd and even resonant tunneling predicted theoretically were not observed experimentally.

Combined Use of Residual Dipolar Couplings and Solution X-ray Scattering To Rapidly Probe Rigid-Body Conformational Transitions in a Non-phosphorylatable Active-Site Mutant of the 128 kDa Enzyme I Dimer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takayama, Yuki; Schwieters, Charles D.; Grishaev, Alexander

2012-10-23

The first component of the bacterial phosphotransferase system, enzyme I (EI), is a multidomain 128 kDa dimer that undergoes large rigid-body conformational transitions during the course of its catalytic cycle. Here we investigate the solution structure of a non-phosphorylatable active-site mutant in which the active-site histidine is substituted by glutamine. We show that perturbations in the relative orientations and positions of the domains and subdomains can be rapidly and reliably determined by conjoined rigid-body/torsion angle/Cartesian simulated annealing calculations driven by orientational restraints from residual dipolar couplings and shape and translation information afforded by small- and wide-angle X-ray scattering. Although histidinemore » and glutamine are isosteric, the conformational space available to a Gln side chain is larger than that for the imidazole ring of His. An additional hydrogen bond between the side chain of Gln189 located on the EIN{sup {alpha}/{beta}} subdomain and an aspartate (Asp129) on the EIN{sup {alpha}} subdomain results in a small ({approx}9{sup o}) reorientation of the EIN{sup {alpha}} and EIN{sup {alpha}/{beta}} subdomains that is in turn propagated to a larger reorientation ({approx}26{sup o}) of the EIN domain relative to the EIC dimerization domain, illustrating the positional sensitivity of the EIN domain and its constituent subdomains to small structural perturbations.« less

Influence of dipolar interactions on the superparamagnetic relaxation time of γ-Fe2O3

NASA Astrophysics Data System (ADS)

Labzour, A.; Housni, A.; Limame, K.; Essahlaoui, A.; Sayouri, S.

2017-03-01

Influence of dipolar interactions on the Néel superparamagnetic relaxation time, τ , of an assembly of ultrafine ferromagnetic particles (γ-Fe2O3 ) with uniaxial anisotropy and of different sizes has been widely studied using Mössbauer technique. These studies, based on different analytical approaches, have shown that τ decreases with increasing interactions between particles. To interpret these results, we propose a model where interaction effects are considered as being due to a constant and external randomly oriented magnetic field B(Ψ, ϕ). The model is based on the resolution of the Fokker-Planck equation (FPE), generalizes previous calculations and gives satisfactory interpretation of the relaxation phenomenon in such systems.

Interlayer-coupled spin vortex pairs and their response to external magnetic fields

NASA Astrophysics Data System (ADS)

Wintz, Sebastian; Bunce, Christopher; Banholzer, Anja; Körner, Michael; Strache, Thomas; Mattheis, Roland; McCord, Jeffrey; Raabe, Jörg; Quitmann, Christoph; Erbe, Artur; Fassbender, Jürgen

2012-06-01

We report on the response of multilayer spin textures to static magnetic fields. Coupled magnetic vortex pairs in trilayer elements (ferromagnetic/nonmagnetic/ferromagnetic) are imaged directly by means of layer-selective magnetic x-ray microscopy. We observe two different circulation configurations with parallel and opposing senses of magnetization rotation at remanence. Upon application of a field, all of the vortex pairs investigated react with a displacement of their cores. For purely dipolar coupled pairs, the individual core displacements are similar to those of an isolated single-layer vortex, but also a noticeable effect of the mutual stray fields is detected. Vortex pairs that are linked by an additional interlayer exchange coupling (IEC), which is either ferromagnetic or antiferromagnetic, mainly exhibit a layer-congruent response. We find that, apart from a possible decoupling at higher fields, these strict IEC vortex pairs can be described by a single-layer model with effective material parameters. This result implies the possibility to design multilayer spin structures with arbitrary effective magnetization.

Effect of interstitial palladium on plasmon-driven charge transfer in nanoparticle dimers.

PubMed

Lerch, Sarah; Reinhard, Björn M

2018-04-23

Capacitive plasmon coupling between noble metal nanoparticles (NPs) is characterized by an increasing red-shift of the bonding dipolar plasmon mode (BDP) in the classical electromagnetic coupling regime. This model breaks down at short separations where plasmon-driven charge transfer induces a gap current between the NPs with a magnitude and separation dependence that can be modulated if molecules are present in the gap. Here, we use gap contained DNA as a scaffold for the growth of palladium (Pd) NPs in the gap between two gold NPs and investigate the effect of increasing Pd NP concentration on the BDP mode. Consistent with enhanced plasmon-driven charge transfer, the integration of discrete Pd NPs depolarizes the capacitive BDP mode over longer interparticle separations than is possible in only DNA-linked Au NPs. High Pd NP densities in the gap increases the gap conductance and induces the transition from capacitive to conductive coupling.

Composite-pulse and partially dipolar dephased multiCP for improved quantitative solid-state 13C NMR

NASA Astrophysics Data System (ADS)

Duan, Pu; Schmidt-Rohr, Klaus

2017-12-01

Improved multiple cross polarization (multiCP) pulse sequences for quickly acquiring quantitative 13C NMR spectra of organic solids are presented. Loss of 13C magnetization due to imperfect read-out and storage pulses in multiCP has been identified as a significant mechanism limiting polarization enhancement for 13C sites with weak couplings to 1H. This problem can be greatly reduced by composite 90° pulses with non-orthogonal phases that flip the magnetization onto the spin-lock field and back to the longitudinal direction for the 1H repolarization period; the observed loss is <3% for over ±10 kHz resonance offset and up to 20% flip-angle error. This composite-pulse multiCP (ComPmultiCP) sequence consistently provides performance superior to that of conventional multiCP, without any trade-off. The longer total CP time enabled by the composite pulses allows for a wider amplitude ramp during CP, which decreases the sensitivity to Hartmann-Hahn mismatch by a factor of two, with a <7% root-mean-square deviation within a 1-dB range for Boc-alanine. In samples with very short T1ρ, under-polarization of non-protonated carbons can be compensated by slight dipolar dephasing of CHn signals resulting from relatively weak decoupling during the Hahn spin echo period before detection. Quantitative spectra have been obtained by ComPmultiCP for low-crystallinity branched polyethylene at 4.5 kHz MAS, and in combination with partial dipolar dephasing for soil organic matter at 14 kHz MAS.

Fluid transport by dipolar vortices

NASA Astrophysics Data System (ADS)

I, Eames; J.-B, Flór

1998-08-01

The transport properties of dipolar vortices propagating on an f-plane are studied experimentally by examining the distortion of a series of material surfaces. The observations are compared with a model based on characterising the flow around the dipole as irrotational flow past a rigid cylinder of volume V. Measurements made of the volume of fluid permanently displaced forward by the vortices, agree to within 20% of that predicted by the proposition of Darwin [Darwin, C., 1953. A note on hydrodynamics. Proc. Cambridge Philos. Soc., 49, 342-354], namely that the vortex will displace a volume CMV forward, where CM=1 for a Lamb's dipole. The results are applied to examine fluid transport by dipolar vortices propagating on the β-plane, where the ambient potential vorticity field causes easterly propagating dipolar vortices to meander sinusoidally between the North and South. We demonstrate that as the vortex moves between the North and South, it exchanges a volume CMV sin α by the drift effect (where α is the angle between the velocity of the dipole and the material surface), which is generally larger than that attributed to other mechanisms such as lobe shedding. The results are applied to give new insight to the effect of vortices in enhancing diffusion, and the secondary flow generated by the transport of ambient potential vorticity.

Dipolar DC Collisional Activation in a "Stretched" 3-D Ion Trap: The Effect of Higher Order Fields on rf-Heating

NASA Astrophysics Data System (ADS)

Prentice, Boone M.; McLuckey, Scott A.

2012-04-01

Applying dipolar DC (DDC) to the end-cap electrodes of a 3-D ion trap operated with a bath gas at roughly 1 mTorr gives rise to `rf-heating' and can result in collision-induced dissociation (CID). This approach to ion trap CID differs from the conventional single-frequency resonance excitation approach in that it does not rely on tuning a supplementary frequency to coincide with the fundamental secular frequeny of the precursor ion of interest. Simulations using the program ITSIM 5.0 indicate that application of DDC physically displaces ions solely in the axial (inter end-cap) dimension whereupon ion acceleration occurs via power absorption from the drive rf. Experimental data shows that the degree of rf-heating in a stretched 3-D ion trap is not dependent solely on the ratio of the dipolar DC voltage/radio frequency (rf) amplitude, as a model based on a pure quadrupole field suggests. Rather, ion temperatures are shown to increase as the absolute values of the dipolar DC and rf amplitude both decrease. Simulations indicate that the presence of higher order multi-pole fields underlies this unexpected behavior. These findings have important implications for the use of DDC as a broad-band activation approach in multi-pole traps.

Dipolar excitation in the third stability region.

PubMed

Konenkov, Nikolai V; Chernyak, Eugenii Ya; Stepanov, Vladimir A

Dipole resonant excitation of ions creates instability bands which follow iso-β lines where β is the characteristic exponent (stability parameter). Instability bands are exited most effectively on the fundamental frequency π= βΩ/2. Here π is the angle resonance frequency of the dipolar voltage applied to x or y pair rods of the analyzer, and Ω is the angle frequency of the main drive voltage. Our goal is to study the mass peak shape in the third stability region with dipolar resonance excitation of the instability band with respect to the resonance frequency π and the dipolar potential amplitude. Numerical integration of the ion motion equations with a given ion source emittance is used to investigate peak shapes and ion transmission. We show that it is possible to vary the resolution power at any part of the third stability region. A change of the dipolar potential phase leads to a periodical variation of the resolution with period π.The most effective dipolar excitation in the y direction is along βy near the stability boundary. The mass peak shape is calculated also for a quadrupole with round rods. The best peak shape (small tails and high resolution) takes place for the rod set with r/r0=1.130. Dipolar excitation increases the transmission by approximately 5-10% at a given resolution.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Herman, Michael F.; Currier, Robert P.; Peery, Travis B.

Intermolecular coupling of dipole moments is studied for a model system consisting of two diatomic molecules (AB monomers) arranged co-linearly and which can form non-covalently bound dimers. The dipolar coupling is a function of the bond length in each molecule as well as of the distance between the centers-of-mass of the two molecules. The calculations show that intermolecular coupling of the vibrations results in an isotope-dependent modification of the AB-AB intermolecular potential. This in turn alters the energies of the low-lying bound states of the dimers, producing isotope-dependent changes in the AB-AB dimer partition function. Explicit inclusion of intermolecular vibrationalmore » coupling then changes the predicted gas-dimer isotopic fractionation. In addition, a mass dependence in the intermolecular potential can also result in changes in the number of bound dimer states in an equilibrium mixture. This in turn leads to a significant dimer population shift in the model monomer-dimer equilibrium system considered here. Finally, the results suggest that intermolecular coupling terms should be considered when probing the origins of isotopic fractionation.« less

Configurations of base-pair complexes in solutions. [nucleotide chemistry

NASA Technical Reports Server (NTRS)

Egan, J. T.; Nir, S.; Rein, R.; Macelroy, R.

1978-01-01

A theoretical search for the most stable conformations (i.e., stacked or hydrogen bonded) of the base pairs A-U and G-C in water, CCl4, and CHCl3 solutions is presented. The calculations of free energies indicate a significant role of the solvent in determining the conformations of the base-pair complexes. The application of the continuum method yields preferred conformations in good agreement with experiment. Results of the calculations with this method emphasize the importance of both the electrostatic interactions between the two bases in a complex, and the dipolar interaction of the complex with the entire medium. In calculations with the solvation shell method, the last term, i.e., dipolar interaction of the complex with the entire medium, was added. With this modification the prediction of the solvation shell model agrees both with the continuum model and with experiment, i.e., in water the stacked conformation of the bases is preferred.

Electroencephalography (EEG) forward modeling via H(div) finite element sources with focal interpolation.

PubMed

Pursiainen, S; Vorwerk, J; Wolters, C H

2016-12-21

The goal of this study is to develop focal, accurate and robust finite element method (FEM) based approaches which can predict the electric potential on the surface of the computational domain given its structure and internal primary source current distribution. While conducting an EEG evaluation, the placement of source currents to the geometrically complex grey matter compartment is a challenging but necessary task to avoid forward errors attributable to tissue conductivity jumps. Here, this task is approached via a mathematically rigorous formulation, in which the current field is modeled via divergence conforming H(div) basis functions. Both linear and quadratic functions are used while the potential field is discretized via the standard linear Lagrangian (nodal) basis. The resulting model includes dipolar sources which are interpolated into a random set of positions and orientations utilizing two alternative approaches: the position based optimization (PBO) and the mean position/orientation (MPO) method. These results demonstrate that the present dipolar approach can reach or even surpass, at least in some respects, the accuracy of two classical reference methods, the partial integration (PI) and St. Venant (SV) approach which utilize monopolar loads instead of dipolar currents.

Relative Timing of Substorm-Associated Processes in the Near-Earth Magnetotail and Development of Auroral Onset Arc

NASA Astrophysics Data System (ADS)

Miyashita, Y.; Ieda, A.; Machida, S.; Hiraki, Y.; Angelopoulos, V.; McFadden, J. P.; Auster, H. U.; Mende, S. B.; Donovan, E.; Larson, D. E.

2014-12-01

We have studied the relative timing of the processes in the near-Earth magnetotail and development of auroral onset arc at the beginning of the expansion phase, based on substorm events observed by the THEMIS spacecraft and ground-based all-sky imagers. The THEMIS all-sky imagers can observe auroras over a wide area with temporal and spacial resolutions higher than spacecraft-borne cameras. This enables us to investigate the timing of auroral development in more detail than before. A few min after the appearance and intensification of an auroral onset arc, it begins to form wave-like structure. Then auroral poleward expansion begins another few min later. THEMIS magnetotail observations clearly show that magnetic reconnection is initiated at X~-20 Re at least 1-2 min before the intensification of auroral onset arc. Then low-frequency waves are excited in the plasma sheet at X~-10 Re 2 min before dipolarization, which is simultaneous with the formation of auroral wave-like structure. Dipolarization begins at the same time as the auroral poleward expansion. These results suggest that near-Earth magnetic reconnection plays some role in the development of dipolarization and auroral onset arc.

Low-Frequency Waves in the Near-Earth Magnetotail before Substorm Expansion Onsets

NASA Astrophysics Data System (ADS)

Miyashita, Y.; Saito, M. H.; Hiraki, Y.; Machida, S.

2013-12-01

Magnetic reconnection and dipolarization, which occur in the near-Earth magnetotail just before substorm expansion onsets, are important processes for the substorm triggering. To understand the triggering of these processes, we have investigated low-frequency waves that were observed in the near-Earth magnetotail before onsets, by performing statistical analysis based on Geotail observations and case studies based on multi-point THEMIS and Geotail observations. Here we focused our examination on ~10 min interval before onsets. We find that small-amplitude Alfven and slow-mode magnetosonic waves with a period of ~1 to 2 min continuously exist for more than 10 min before onsets. Such waves are seen not only in the initial dipolarization region but also midway between the magnetic reconnection and initial dipolarization regions. It seems that the amplitudes of the waves are larger in the off-equator plasma sheet and the plasma sheet boundary layer than at the magnetic equator and in the lobe. After onsets the waves considerably amplify in the plasma sheet. These results may imply that instabilities already begin to grow gradually in a wide region during the substorm growth phase, while their explosive growth begins in localized regions just before onsets.

Spin-locking and cross-polarization under magic-angle spinning of uniformly labeled solids.

PubMed

Hung, Ivan; Gan, Zhehong

2015-07-01

Spin-locking and cross-polarization under magic-angle spinning are investigated for uniformly (13)C and (15)N labeled solids. In particular, the interferences from chemical shift anisotropy, and (1)H heteronuclear and (13)C homonuclear dipolar couplings are identified. The physical origin of these interferences provides guidelines for selecting the best (13)C and (15)N polarization transfer rf fields. Optimal settings for both the zero- and double-quantum cross-polarization transfer mechanisms are recommended. Copyright © 2015 Elsevier Inc. All rights reserved.

Contribution of Dipolar Coupling to the Mechanism of the Triplet-Triplet Energy Transfer Process at Long Distances: A Doluble Resonance and Laser Line Narrowing Study.

DTIC Science & Technology

1986-12-16

COVERED 14. DATE OF REPORT (Year, Month, Day) 15. PAGE COUNT Technical Report FROM TO December 16, 1986 29 16 SUPPLEMENTARY NOTATION Acta Physica ... Polonica , in press. 17. COSATI CODES 18. SUBJECT TERMS (Continue on reverse if inecessary and identify by block number) FIELD GROUP SUB-GROUP Energy Transfer...Chan-Lon Yang and M. A. EI-Sayed Department of Chemistry and Biochemistry University of California Los Angeles, California 90024 Acts Physics Polonica

Quantitative structure parameters from the NMR spectroscopy of quadrupolar nuclei

DOE PAGES

Perras, Frederic A.

2015-12-15

Here, nuclear magnetic resonance (NMR) spectroscopy is one of the most important characterization tools in chemistry, however, 3/4 of the NMR active nuclei are underutilized due to their quadrupolar nature. This short review centers on the development of methods that use solid-state NMR of quadrupolar nuclei for obtaining quantitative structural information. Namely, techniques using dipolar recoupling as well as the resolution afforded by double-rotation are presented for the measurement of spin–spin coupling between quadrupoles, enabling the measurement of internuclear distances and connectivities.

Carrier-envelope phase effects for a dipolar molecule interacting with two-color pump-probe laser pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng Taiwang; Brown, Alex

2004-12-01

The interaction of a two-level dipolar molecule with two laser pulses, where one laser's frequency is tuned to the energy level separation (pump laser) while the second laser's frequency is extremely small (probe laser), is investigated. A dipolar molecule is one with a nonzero difference between the permanent dipole moments of the molecular states. As shown previously [A. Brown, Phys. Rev. A 66, 053404 (2002)], the final population transfer between the two levels exhibits a dependence on the carrier-envelope phase of the probe laser. Based on the rotating-wave approximation (RWA), an effective Hamiltonian is derived to account for the basicmore » characteristics of the carrier-envelope phase dependence effect. By analysis of the effective Hamiltonian, scaling properties of the system are found with regard to field strengths, pulse durations, and frequencies. According to these scaling properties, the final-state population transfer can be controlled by varying the carrier-envelope phase of the probe laser field using lasers with weak field strengths (low intensities) and relatively long pulse durations. In order to examine the possible roles of background states, the investigation is extended to a three-level model. It is demonstrated that the carrier-envelope phase effect still persists in a well-defined manner even when neighboring energy levels are present. These results illustrate the potential of utilizing excitation in dipolar molecules as a means of measuring the carrier-envelope phase of a laser pulse or if one can manipulate the carrier envelope phase, as a method of controlling population transfer in dipolar molecules. The results also suggest that the carrier-envelope phases must be taken into account properly when performing calculations involving pump-probe excitation schemes with laser frequencies which differ widely in magnitude.« less

Structures and dynamics in a two-dimensional dipolar dust particle system

NASA Astrophysics Data System (ADS)

Hou, X. N.; Liu, Y. H.; Kravchenko, O. V.; Lapushkina, T. A.; Azarova, O. A.; Chen, Z. Y.; Huang, F.

2018-05-01

The effects of electric dipole moment, the number of dipolar particles, and system temperature on the structures and dynamics of a dipolar dust particle system are studied by molecular dynamics simulations. The results show that the larger electric dipole moment is favorable for the formation of a long-chain structure, the larger number of dipolar dust particles promotes the formation of the multi-chain structure, and the higher system temperature can cause higher rotation frequency. The trajectories, mean square displacement (MSD), and the corresponding spectrum functions of the MSDs are also calculated to illustrate the dynamics of the dipolar dust particle system, which is also closely related to the growth of dust particles. Some simulations are qualitatively in agreement with our experiments and can provide a guide for the study on dust growth, especially on the large-sized particles.

Conformational response of the phosphatidylcholine headgroup to bilayer surface charge: torsion angle constraints from dipolar and quadrupolar couplings in bicelles.

PubMed

Semchyschyn, Darlene J; Macdonald, Peter M

2004-02-01

The effects of bilayer surface charge on the conformation of the phosphocholine group of phosphatidylcholine were investigated using a torsion angle analysis of quadrupolar and dipolar splittings in, respectively, (2)H and (13)C NMR spectra of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) labelled in the phosphocholine group with either deuterons (POPC-alpha-d(2), POPC-beta-d(2) and POPC-gamma-d(9)) or carbon-13 (POPC-alpha-(13)C and POPC-alphabeta-(13)C(2)) and incorporated into magnetically aligned bicelles containing various amounts of either the cationic amphiphile 1,2-dimyristoyl-3-trimethylammoniumpropane (DMTAP) or the anionic amphiphile 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol (DMPG). Three sets of quadrupolar splittings, one from each of the three deuteron labelling positions, and three sets of dipolar splittings ((13)C(alpha)-(31)P, (13)C(alpha)-(13)C(beta), (13)C(beta)-(14)N), were measured at each surface charge, along with the (31)P residual chemical shift anisotropy. The torsion angle analysis assumed fast anisotropic rotation of POPC about its long molecular axis, thus projecting all NMR interactions onto that director axis of motion. Dipolar, quadrupolar and chemical shift anisotropies were calculated as a function of the phosphocholine internal torsion angles by first transforming into a common reference frame affixed to the phosphocholine group prior to motional averaging about the director axis. A comparison of experiment and calculation provided the two order parameters specifying the director orientation relative to the molecule, plus the torsion angles alpha(3), alpha(4) and alpha(5). Surface charge was found to have little effect on the torsion angle alpha(5) (rotations about C(alpha)-C(beta)), but to have large and inverse effects on torsion angles alpha(3) [rotations about P-O(11)] and alpha(4) [rotations about O(11)-C(alpha)], yielding a net upwards tilt of the P-N vector in the presence of cationic surface charge, and a downwards tilt in the presence of anionic surface charge, relative to neutrality. Copyright 2004 John Wiley & Sons, Ltd.

Magnetic Field Dipolarization and Its Associated Ion Flux Variations in the Inner Magnetosphere: Simultaneous Observations by Arase and Michibiki Satellites

NASA Astrophysics Data System (ADS)

Nose, M.; Matsuoka, A.; Kasahara, S.; Yokota, S.; Higashio, N.; Koshiishi, H.; Imajo, S.; Teramoto, M.; Nomura, R.; Fujimoto, A.; Keika, K.; Tanaka, Y.; Shinohara, M.; Shinohara, I.; Yoshizumi, M.

2017-12-01

Recent satellite observations by MDS-1 and Van Allen Probes statistically revealed that magnetic field dipolarization can be detected over a wide range of L in the deep inner magnetosphere (i.e., L = 3.5-6.5, which is far inside the geosynchronous altitude). It is accompanied by magnetic field fluctuations having a characteristic timescale of a few to 10 s, which is comparable to the local gyroperiod of O+ ions. These magnetic field fluctuations are considered to cause nonadiabatic local acceleration of ions. In this study, we intend to confirm the above-mentioned characteristics of magnetic field dipolarization in the inner magnetosphere, using the magnetic field data and the energetic ion flux data measured by the Exploration of energization and Radiation in Geospace (ERG) "Arase" satellite. The Arase satellite was launched on December 20, 2016 into an elliptical orbit having an apogee of 6.0 Re, a perigee of 440 km altitude, an orbital period of 9.5 h, and an orbital inclination of 32 degrees. During the first magnetic storm of March 27, 2017 after Arase started scientific operation, Arase observes clear dipolarization signatures around 1500 UT at L 4.6 and MLT 5.7 hr. Strong magnetic field fluctuations are embedded in the magnetic field dipolarization and their characteristic frequency is close to the local gyrofrequency of O+ ions. Both H+ and O+ flux enhancements are observed in accordance with the dipolarization. These results are consistent with the previous results. In this event, the Quasi-Zenith Satellite (QZS)-1 "Michibiki" satellite was located at L 7.0 and MLT 23.8 hr, and observes similar dipolarization signatures with a few minute time difference. Simultaneous observations by both Arase and Michibiki provides us a unique opportunity to investigate how fast and wide the dipolarization propagates in the inner magnetosphere. In the presentation, we will show detailed analysis results of the dipolarization event on March 27, 2017 as well as similar events.

Cluster analysis in systems of magnetic spheres and cubes

NASA Astrophysics Data System (ADS)

Pyanzina, E. S.; Gudkova, A. V.; Donaldson, J. G.; Kantorovich, S. S.

2017-06-01

In the present work we use molecular dynamics simulations and graph-theory based cluster analysis to compare self-assembly in systems of magnetic spheres, and cubes where the dipole moment is oriented along the side of the cube in the [001] crystallographic direction. We show that under the same conditions cubes aggregate far less than their spherical counterparts. This difference can be explained in terms of the volume of phase space in which the formation of the bond is thermodynamically advantageous. It follows that this volume is much larger for a dipolar sphere than for a dipolar cube.

Extended Bose-Hubbard model with dipolar and contact interactions

NASA Astrophysics Data System (ADS)

Biedroń, Krzysztof; Łącki, Mateusz; Zakrzewski, Jakub

2018-06-01

We study the phase diagram of the one-dimensional boson gas trapped inside an optical lattice with contact and dipolar interaction, taking into account next-nearest terms for both tunneling and interaction. Using the density-matrix renormalization group, we calculate how the locations of phase transitions change with increasing dipolar interaction strength for average density ρ =1 . Furthermore, we show the emergence of pair-correlated phases for a large dipolar interaction strength and ρ ≥2 , including a supersolid phase with an incommensurate density wave ordering manifesting the corresponding spontaneous breaking of the translational symmetry.

Numerical simulations of motion-insensitive diffusion imaging based on the distant dipolar field effects.

PubMed

Lin, Tao; Sun, Huijun; Chen, Zhong; You, Rongyi; Zhong, Jianhui

2007-12-01

Diffusion weighting in MRI is commonly achieved with the pulsed-gradient spin-echo (PGSE) method. When combined with spin-warping image formation, this method often results in ghosts due to the sample's macroscopic motion. It has been shown experimentally (Kennedy and Zhong, MRM 2004;52:1-6) that these motion artifacts can be effectively eliminated by the distant dipolar field (DDF) method, which relies on the refocusing of spatially modulated transverse magnetization by the DDF within the sample itself. In this report, diffusion-weighted images (DWIs) using both DDF and PGSE methods in the presence of macroscopic sample motion were simulated. Numerical simulation results quantify the dependence of signals in DWI on several key motion parameters and demonstrate that the DDF DWIs are much less sensitive to macroscopic sample motion than the traditional PGSE DWIs. The results also show that the dipolar correlation distance (d(c)) can alter contrast in DDF DWIs. The simulated results are in good agreement with the experimental results reported previously.

Mesoscale magnetism

DOE PAGES

Hoffmann, Axel; Schultheiß, Helmut

2014-12-17

Magnetic interactions give rise to a surprising amount of complexity due to the fact that both static and dynamic magnetic properties are governed by competing short-range exchange interactions and long-range dipolar coupling. Even though the underlying dynamical equations are well established, the connection of magnetization dynamics to other degrees of freedom, such as optical excitations, charge and heat flow, or mechanical motion, make magnetism a mesoscale research problem that is still wide open for exploration. Synthesizing magnetic materials and heterostructures with tailored properties will allow to take advantage of magnetic interactions spanning many length-scales, which can be probed with advancedmore » spectroscopy and microscopy and modeled with multi-scale simulations. Finally, this paper highlights some of the current basic research topics in mesoscale magnetism, which beyond their fundamental science impact are also expected to influence applications ranging from information technologies to magnetism based energy conversion.« less

Magnetosphere-ionosphere coupling during substorm onset

NASA Technical Reports Server (NTRS)

Maynard, N. C.; Burke, W. J.; Erickson, G. M.; Basinka, E. M.; Yahnin, A. G.

1996-01-01

Through the analysis of a combination of CRRES satellite measurements and ground-based measurements, an empirical scenario was developed for the onset of substorms. The process develops from ripples at the inner edge of the plasma sheet associated with dusk to dawn excursions of the electric field, prior to the beginning of dipolarization. The importance of Poynting flux is considered. Substorms develop when significant amounts of energy flow in both directions with the second cycle stronger than the initial cycle. Pseudobreakups occur when the energy flowing in both directions is weak or out of phase. The observations indicate that the dusk to dawn excursions of the cross-tail electric field correlate with changes in currents and particle energies observed by CRRES, and with ultra low frequency wave activity observed on the ground. Magnetic signatures of field aligned current filaments, associated with the substorm current wedge were observed to be initiated by the process.

Synthesis and evaluation of changes induced by solvent and substituent in electronic absorption spectra of some azo disperse dyes

NASA Astrophysics Data System (ADS)

Mohammadi, Asadollah; Yazdanbakhsh, Mohammad Reza; Farahnak, Lahya

2012-04-01

Five azo disperse dyes were prepared by diazotizing 4'-aminoacetophenone and p-anisidine and coupling with varies N-alkylated aromatic amines. Characterization of the dyes was carried out by using UV-vis, FTIR and 1H NMR spectroscopic techniques. The electronic absorption spectra of dyes are determined at room temperature in fifteen solvents with different polarities. The solvent dependent maximum absorption band shifts, were investigated using dielectric constant (ɛ), refractive index (n) and Kamlet-Taft polarity parameters (hydrogen bond donating ability (α), hydrogen bond accepting ability (β) and dipolarity/polarizability polarity scale (π*)). Acceptable agreement was found between the maximum absorption band of dyes and solvent polarity parameters especially with π*. The effect of substituents of coupler and/or diazo component on the color of dyes was investigated. The effects of acid and base on the visible absorption maxima of the dyes are also reported.

Stepwise π-extension of meso-alkylidenyl porphyrins through sequential 1,3-dipolar cycloaddition and redox reactions.

PubMed

Park, Dowoo; Jeong, Seung Doo; Ishida, Masatoshi; Lee, Chang-Hee

2014-08-25

Several regioselectively π-extended, pyrrole fused porphyrinoids have been synthesized by the 1,3-dipolar cycloaddition of meso-alkylidene-(benzi)porphyrins. Pd(II) complexes gave oxidation resistant, bis-pyrrole fused adducts. The repeated 1,3-dipolar cycloaddition followed by oxidation-reduction of pentaphyrin analogs afforded π-extended porphyrin analogs.

Co- and contra-directional vertical coupling between ferromagnetic layers with grating for short-wavelength spin wave generation

NASA Astrophysics Data System (ADS)

Graczyk, Piotr; Zelent, Mateusz; Krawczyk, Maciej

2018-05-01

The possibility to generate short spin waves (SWs) is of great interest in the field of magnonics nowadays. We present an effective and technically affordable way of conversion of long SWs, which may be generated by conventional microwave antenna, to the short, sub-micrometer waves. It is achieved by grating-assisted resonant dynamic dipolar interaction between two ferromagnetic layers separated by some distance. We analyze criteria for the optimal conversion giving a semi-analytical approach for the coupling coefficient. We show by the numerical calculations the efficient energy transfer between layers which may be either of co-directional or contra-directional type. Such a system may operate either as a short spin wave generator or a frequency filter, moving forward possible application of magnonics.

Phase locking of vortex cores in two coupled magnetic nanopillars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Qiyuan; Liu, Xianyin; Zheng, Qi

2014-11-15

Phase locking dynamics of the coupled vortex cores in two identical magnetic spin valves induced by spin-polarized current are studied by means of micromagnetic simulations. Our results show that the available current range of phase locking can be expanded significantly by the use of constrained polarizer, and the vortices undergo large orbit motions outside the polarization areas. The effects of polarization areas and dipolar interaction on the phase locking dynamics are studied systematically. Phase locking parameters extracted from simulations are discussed by theoreticians. The dynamics of vortices influenced by spin valve geometry and vortex chirality are discussed at last. Thismore » work provides deeper insights into the dynamics of phase locking and the results are important for the design of spin-torque nano-oscillators.« less

Direct Simulation of Magnetic Resonance Relaxation Rates and Line Shapes from Molecular Trajectories

PubMed Central

Rangel, David P.; Baveye, Philippe C.; Robinson, Bruce H.

2012-01-01

We simulate spin relaxation processes, which may be measured by either continuous wave or pulsed magnetic resonance techniques, using trajectory-based simulation methodologies. The spin–lattice relaxation rates are extracted numerically from the relaxation simulations. The rates obtained from the numerical fitting of the relaxation curves are compared to those obtained by direct simulation from the relaxation Bloch–Wangsness–Abragam– Redfield theory (BWART). We have restricted our study to anisotropic rigid-body rotational processes, and to the chemical shift anisotropy (CSA) and a single spin–spin dipolar (END) coupling mechanisms. Examples using electron paramagnetic resonance (EPR) nitroxide and nuclear magnetic resonance (NMR) deuterium quadrupolar systems are provided. The objective is to compare those rates obtained by numerical simulations with the rates obtained by BWART. There is excellent agreement between the simulated and BWART rates for a Hamiltonian describing a single spin (an electron) interacting with the bath through the chemical shift anisotropy (CSA) mechanism undergoing anisotropic rotational diffusion. In contrast, when the Hamiltonian contains both the chemical shift anisotropy (CSA) and the spin–spin dipolar (END) mechanisms, the decay rate of a single exponential fit of the simulated spin–lattice relaxation rate is up to a factor of 0.2 smaller than that predicted by BWART. When the relaxation curves are fit to a double exponential, the slow and fast rates extracted from the decay curves bound the BWART prediction. An extended BWART theory, in the literature, includes the need for multiple relaxation rates and indicates that the multiexponential decay is due to the combined effects of direct and cross-relaxation mechanisms. PMID:22540276

Constraining the dipolar magnetic field of M82 X-2 by the accretion model

NASA Astrophysics Data System (ADS)

Chen, Wen-Cong

2017-02-01

Recently, ultraluminous X-ray source (ULX) M82 X-2 has been identified to be an accreting neutron star, which has a P = 1.37 s spin period, and is spinning up at a rate dot{P}=-2.0× 10^{-10} s s^{-1}. Interestingly, its isotropic X-ray luminosity Liso = 1.8 × 1040 erg s- 1 during outbursts is 100 times the Eddington limit for a 1.4 M⊙ neutron star. In this Letter, based on the standard accretion model we attempt to constrain the dipolar magnetic field of the pulsar in ULX M82 X-2. Our calculations indicate that the accretion rate at the magnetospheric radius must be super-Eddington during outbursts. To support such a super-Eddington accretion, a relatively high multipole field ( ≳ 1013 G) near the surface of the accretor is invoked to produce an accreting gas column. However, our constraint shows that the surface dipolar magnetic field of the pulsar should be in the range of 1.0-3.5 × 1012 G. Therefore, our model supports that the neutron star in ULX M82 X-2 could be a low-magnetic-field magnetar (proposed by Tong) with a normal dipolar field (˜1012 G) and relatively strong multipole field. For the large luminosity variations of this source, our scenario can also present a self-consistency interpretation.

Spectroscopic studies of transition metal ions in molten alkali metal carboxylates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maroni, V.A.; Maciejewski, M.L.

Electronic absorption and C-13 NMR spectroscopic studies were carried out to investigate the structure of (i) alkali metal formate (Fm) and acetate (Ac) eutectic melts and (ii) solutions of 3d transition metal (TM) cations in these eutectics. Measurements were made over the temperature range 90..-->..190/sup 0/C. The most stable oxidation states of the individual TMs in the Fm and Ac eutectics were: Ti/sup 3 +/, V/sup 3 +/, VO/sup 2 +/, Cr/sup 3 +/, Mn/sup 2 +/, Fe/sup 2 +/, Co/sup 2 +/, Ni/sup 2 +/, and Cu/sup 2 +/. The ligand field absorption spectra obtained in these carboxylate meltsmore » bore a consistent resemblance to the spectra of these same cations in aqueous media, but the absorptivities were generally higher than are observed for the hexaquo complexes. The results were interpreted in terms of the existence of bidentate coordination in some (if not all) cases, leading to noncentrosymmetric complexation geometries. Key results of the NMR measurements included the apparent observation of two different carboxylate anion environments in Ni/sup 2 +/ solutions. C-13 spin-lattice relaxation of the carboxylate anions in the TM-free eutectics was found to be controlled by dipolar coupling to another nucleus. In the TM-containing solutions, the spin-lattice relaxation times were reduced by a factor of 10 to 1000, evidencing the expected shift to electron-nuclear dipolar coupling. Activation energies for viscous flow derived from the spin-lattice relaxation measurements on TM-free melts were in the 10..-->..11 kcal/mol range, reflecting the highly ordered, glassy nature of the eutectics studied.« less

Direct Investigation of Slow Correlated Dynamics in Proteins via Dipolar Interactions

PubMed Central

Fenwick, R. Bryn; Schwieters, Charles D.; Vögeli, Beat

2016-01-01

The synchronization of native state motions as they transition between microstates influences catalysis kinetics, mediates allosteric interactions and reduces the conformational entropy of proteins. However, it has proven difficult to describe native microstates because they are usually minimally frustrated and may interconvert on the μs-ms time scale. Direct observation of concerted equilibrium fluctuations would therefore be an important tool for describing protein native states. Here we propose a strategy that relates NMR cross-correlated relaxation (CCR) rates between dipolar interactions to residual dipolar couplings (RDCs) of individual consecutive HN–N and Hα–Cα bonds, which act as a proxy for the peptide planes and the side chains respectively. Using Xplor-NIH ensemble structure calculations restrained with the RDC and CCR data we observe collective motions on time scales slower than nanoseconds in the backbone for GB3. To directly access the correlations from CCR we develop a structure-free data analysis. The resulting dynamic correlation map is consistent with the ensemble-restrained simulations and reveals a complex network. In general we find that the bond motions are on average slightly correlated, and that the local environment dominates many observations. Despite this, some patterns are typical over entire secondary structure elements. In the β-sheet, nearly all bonds are weakly correlated and there is an approximately binary alternation in correlation intensity corresponding to the solvent exposure/shielding alternation of the side chains. For α-helices there is also a weak correlation in the HN-N bonds and the degree of correlation involving Hα-Cα bonds is directly affected by side-chain fluctuations, while loops show complex and non-uniform behavior. PMID:27331619

Direct 1H NMR evidence of spin-rotation coupling as a source of para → ortho-H2 conversion in diamagnetic solvents.

PubMed

Terenzi, Camilla; Bouguet-Bonnet, Sabine; Canet, Daniel

2017-04-21

At ambient temperature, conversion from 100% enriched para-hydrogen (p-H 2 ; singlet state) to ortho-hydrogen (o-H 2 ; triplet state) leads necessarily to the thermodynamic equilibrium proportions: 75% of o-H 2 and 25% of p-H 2 . When p-H 2 is dissolved in a diamagnetic organic solvent, conversion is very slow and can be considered as arising from nuclear spin relaxation phenomena. A first relaxation mechanism, specific to the singlet state and involving a combination of auto-correlation and cross correlation spectral densities, can be retained: randomly fluctuating magnetic fields due to inter-molecular dipolar interactions. We demonstrate here that (i) this dipolar mechanism is not sufficient for accounting for the para→ortho conversion rate, (ii) spin-rotation interaction, an intra-molecular mechanism, behaves similarly to random-field interaction and, thus, may be involved in the singlet relaxation rate. Also, as the para→ortho conversion is monitored by proton nuclear magnetic resonance (NMR) of dissolved o-H 2 (p-H 2 is NMR-silent), one has to account for H 2 exchange between the liquid phase and the gas phase within the NMR tube, as well as for dissolution effects. Experimental evidence of the above statements is brought here in the case of two organic solvents: acetone-d 6 and carbon disulfide. The observed temperature dependence of the para→ortho conversion rate shows that spin-rotation can be the dominant contribution to the p-H 2 relaxation rate in the absence of tangible dipolar interactions. Our findings shed new light on the "mysterious" mechanism of the para→ortho conversion which has been searched for several decades.

The extreme dipolarization during the Galaxy 15 spacecraft anomaly

NASA Astrophysics Data System (ADS)

Loto'aniu, P. T. M.; Redmon, R. J.; Welling, D. T.; Rodriguez, J. V.; Haiducek, J. D.

2016-12-01

The substorm just prior to the Galaxy 15 spacecraft anomaly on 5 April 2010 was intriguing for a number of reasons, including that multiple spacecraft were well located near-midnight to observe the event. Another reason is that the associated dipolarization was one of the most severe ever observed by GOES satellites, even though the solar wind conditions were moderate. In this study, we compare the Galaxy 15 event to other substorms in order to understand why the dipolarization was so extreme. Presented will be simulations from the Space Weather Modeling Framework (SWMF) of different storms and comparisons made to model results for the Galaxy 15 anomaly event. The SWMF does well in predicting some storms, particularly when heavier O+ ions outflowing from the ionosphere are included. However, the SWMF significantly under-predicts the magnitude of the Galaxy 15 event, regardless of the inclusion of a heavy ion outflow model. The model dipolarization occurs around 30 minutes later than the observed event, while the strength of the dipolarization in terms of the magnetic field was not predicted by the model, although, the model does well overall predicting Dst and Kp. We will also present statistical results representing a survey of dipolarizations observed by the GOES spacecraft over a solar cycle when the satellites were located in the near-midnight local time region. The statistical results are used to determine the occurrence rate and characteristics of similar events to the Galaxy 15 dipolarization event.

Vertical Phase Segregation Induced by Dipolar Interactions in Planar Polymer Brushes

DOE PAGES

Mahalik, Jyoti P.; Sumpter, Bobby G.; Kumar, Rajeev

2016-09-13

In this paper, we present a generalized theory for studying structural properties of a planar dipolar polymer brush immersed in a polar solvent. We show that an explicit treatment of the dipolar interactions yields a macroscopic concentration dependent effective “chi” (the Flory–Huggins-like interaction) parameter. Furthermore, it is shown that the concentration dependent chi parameter promotes phase segregation in polymer solutions and brushes so that the polymer-poor phase consists of a finite/nonzero polymer concentration. Such a destabilization of the homogeneous phase by the dipolar interactions appears as vertical phase segregation in a planar polymer brush. In a vertically phase segregated polymermore » brush, the polymer-rich phase near the grafting surface coexists with the polymer-poor phase at the other end. Predictions of the theory are directly compared with prior reported experimental results for dipolar polymers in polar solvents. Excellent agreements with the experimental results are found, hinting that the dipolar interactions play a significant role in vertical phase segregation of planar polymer brushes. We also compare our field theoretical approach with the two-state and other models invoking ad hoc concentration dependence of the chi parameter. Interplay between the short-ranged excluded volume interactions and long-ranged dipolar interactions is shown to play an important role in affecting the vertical phase separation. Finally, effects of mismatch between the dipole moments of the polymer segments and the solvent molecules are investigated in detail.« less

Probing long-range carrier-pair spin–spin interactions in a conjugated polymer by detuning of electrically detected spin beating

PubMed Central

van Schooten, Kipp J.; Baird, Douglas L.; Limes, Mark E.; Lupton, John M.; Boehme, Christoph

2015-01-01

Weakly coupled electron spin pairs that experience weak spin–orbit interaction can control electronic transitions in molecular and solid-state systems. Known to determine radical pair reactions, they have been invoked to explain phenomena ranging from avian magnetoreception to spin-dependent charge-carrier recombination and transport. Spin pairs exhibit persistent spin coherence, allowing minute magnetic fields to perturb spin precession and thus recombination rates and photoreaction yields, giving rise to a range of magneto-optoelectronic effects in devices. Little is known, however, about interparticle magnetic interactions within such pairs. Here we present pulsed electrically detected electron spin resonance experiments on poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) devices, which show how interparticle spin–spin interactions (magnetic-dipolar and spin-exchange) between charge-carrier spin pairs can be probed through the detuning of spin-Rabi oscillations. The deviation from uncoupled precession frequencies quantifies both the exchange (<30 neV) and dipolar (23.5±1.5 neV) interaction energies responsible for the pair's zero-field splitting, implying quantum mechanical entanglement of charge-carrier spins over distances of 2.1±0.1 nm. PMID:25868686

Probing long-range carrier-pair spin–spin interactions in a conjugated polymer by detuning of electrically detected spin beating

DOE PAGES

van Schooten, Kipp J.; Baird, Douglas L.; Limes, Mark E.; ...

2015-04-14

Here, weakly coupled electron spin pairs that experience weak spin–orbit interaction can control electronic transitions in molecular and solid-state systems. Known to determine radical pair reactions, they have been invoked to explain phenomena ranging from avian magnetoreception to spin-dependent charge-carrier recombination and transport. Spin pairs exhibit persistent spin coherence, allowing minute magnetic fields to perturb spin precession and thus recombination rates and photoreaction yields, giving rise to a range of magneto-optoelectronic effects in devices. Little is known, however, about interparticle magnetic interactions within such pairs. Here we present pulsed electrically detected electron spin resonance experiments on poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) devices,more » which show how interparticle spin–spin interactions (magnetic-dipolar and spin-exchange) between charge-carrier spin pairs can be probed through the detuning of spin-Rabi oscillations. The deviation from uncoupled precession frequencies quantifies both the exchange (<30 neV) and dipolar (23.5±1.5 neV) interaction energies responsible for the pair’s zero-field splitting, implying quantum mechanical entanglement of charge-carrier spins over distances of 2.1±0.1 nm.« less

Geometry-dependent distributed polarizability models for the water molecule

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loboda, Oleksandr; Ingrosso, Francesca; Ruiz-López, Manuel F.

2016-01-21

Geometry-dependent distributed polarizability models have been constructed by fits to ab initio calculations at the coupled cluster level of theory with up to noniterative triple excitations in an augmented triple-zeta quality basis set for the water molecule in the field of a point charge. The investigated models include (i) charge-flow polarizabilities between chemically bonded atoms, (ii) isotropic or anisotropic dipolar polarizabilities on oxygen atom or on all atoms, and (iii) combinations of models (i) and (ii). For each model, the polarizability parameters have been optimized to reproduce the induction energy of a water molecule polarized by a point charge successivelymore » occupying a grid of points surrounding the molecule. The quality of the models is ascertained by examining their ability to reproduce these induction energies as well as the molecular dipolar and quadrupolar polarizabilities. The geometry dependence of the distributed polarizability models has been explored by changing bond lengths and HOH angle to generate 125 molecular structures (reduced to 75 symmetry-unique ones). For each considered model, the distributed polarizability components have been fitted as a function of the geometry by a Taylor expansion in monomer coordinate displacements up to the sum of powers equal to 4.« less

Atomic-scale sensing of the magnetic dipolar field from single atoms

NASA Astrophysics Data System (ADS)

Choi, Taeyoung; Paul, William; Rolf-Pissarczyk, Steffen; MacDonald, Andrew J.; Natterer, Fabian D.; Yang, Kai; Willke, Philip; Lutz, Christopher P.; Heinrich, Andreas J.

2017-05-01

Spin resonance provides the high-energy resolution needed to determine biological and material structures by sensing weak magnetic interactions. In recent years, there have been notable achievements in detecting and coherently controlling individual atomic-scale spin centres for sensitive local magnetometry. However, positioning the spin sensor and characterizing spin-spin interactions with sub-nanometre precision have remained outstanding challenges. Here, we use individual Fe atoms as an electron spin resonance (ESR) sensor in a scanning tunnelling microscope to measure the magnetic field emanating from nearby spins with atomic-scale precision. On artificially built assemblies of magnetic atoms (Fe and Co) on a magnesium oxide surface, we measure that the interaction energy between the ESR sensor and an adatom shows an inverse-cube distance dependence (r-3.01±0.04). This demonstrates that the atoms are predominantly coupled by the magnetic dipole-dipole interaction, which, according to our observations, dominates for atom separations greater than 1 nm. This dipolar sensor can determine the magnetic moments of individual adatoms with high accuracy. The achieved atomic-scale spatial resolution in remote sensing of spins may ultimately allow the structural imaging of individual magnetic molecules, nanostructures and spin-labelled biomolecules.

Long-range interactions in magnetic bilayer above the critical temperature

NASA Astrophysics Data System (ADS)

de Souza, R. M. V.; Pereira, T. A. S.; Godoy, M.; de Arruda, A. S.

2018-01-01

In this paper we have studied the stabilization of the long-range order in (z ; x) -plane of two isotropic Heisenberg ferromagnetic monolayers coupled by a short-range exchange interaction (J⊥), by a long range dipole-dipole interactions and a magnetic field. We have applied a magnetic field along of the z-direction to study the thermodynamic properties above the critical temperature. The dispersion relation ω and the magnetization are given as function of dipolar anisotropy parameter defined as Ed =(gμ) 2 S /a3J∥ and for other Hamiltonian parameters, and they are calculated by the double-time Zubarev-Tyablikov Green's functions in the random-phase approximation (RPA). The results show that the system is unstable for values of Ed ≥ 0.012 with external magnetic field ranging between H /J∥ = 0 and 10-3. The instability appears for Ed larger then Edc = 0.0158 with H /J∥ = 10-5, Edc = 0.02885 with H /J∥ = 10-4, and Edc = 0.115 with H /J∥ = 10-3, i.e., a small magnetic field is sufficient to maintain the magnetic order in a greater range of the dipolar interaction.

Observation of Dipolar Spin-Exchange Interactions with Polar Molecules in a Lattice

DTIC Science & Technology

2013-01-01

extend beyond nearest neighbours. This allows coherent spin dynamics to persist even for gases with relatively high entropy and low lattice filling...dynamics to persist even for gases with relatively high entropy and low lat- tice filling. While measured effects of dipolar interactions in ultracold...limits superexchange to nearest-neighbor interactions and requires extremely low temperature and entropy . In contrast, long-range dipolar

Lorentz microscopy sheds light on the role of dipolar interactions in magnetic hyperthermia

NASA Astrophysics Data System (ADS)

Campanini, M.; Ciprian, R.; Bedogni, E.; Mega, A.; Chiesi, V.; Casoli, F.; de Julián Fernández, C.; Rotunno, E.; Rossi, F.; Secchi, A.; Bigi, F.; Salviati, G.; Magén, C.; Grillo, V.; Albertini, F.

2015-04-01

Monodispersed Fe3O4 nanoparticles with comparable size distributions have been synthesized by two different synthesis routes, co-precipitation and thermal decomposition. Thanks to the different steric stabilizations, the described samples can be considered as a model system to investigate the effects of magnetic dipolar interactions on the aggregation states of the nanoparticles. Moreover, the presence of magnetic dipolar interactions can strongly affect the nanoparticle efficiency as a hyperthermic mediator. In this paper, we present a novel way to visualize and map the magnetic dipolar interactions in different kinds of nanoparticle aggregates by the use of Lorentz microscopy, an easy and reliable in-line electron holographic technique. By exploiting Lorentz microscopy, which is complementary to the magnetic measurements, it is possible to correlate the interaction degrees of magnetic nanoparticles with their magnetic behaviors. In particular, we demonstrate that Lorentz microscopy is successful in visualizing the magnetic configurations stabilized by dipolar interactions, thus paving the way to the comprehension of the power loss mechanisms for different nanoparticle aggregates.Monodispersed Fe3O4 nanoparticles with comparable size distributions have been synthesized by two different synthesis routes, co-precipitation and thermal decomposition. Thanks to the different steric stabilizations, the described samples can be considered as a model system to investigate the effects of magnetic dipolar interactions on the aggregation states of the nanoparticles. Moreover, the presence of magnetic dipolar interactions can strongly affect the nanoparticle efficiency as a hyperthermic mediator. In this paper, we present a novel way to visualize and map the magnetic dipolar interactions in different kinds of nanoparticle aggregates by the use of Lorentz microscopy, an easy and reliable in-line electron holographic technique. By exploiting Lorentz microscopy, which is complementary to the magnetic measurements, it is possible to correlate the interaction degrees of magnetic nanoparticles with their magnetic behaviors. In particular, we demonstrate that Lorentz microscopy is successful in visualizing the magnetic configurations stabilized by dipolar interactions, thus paving the way to the comprehension of the power loss mechanisms for different nanoparticle aggregates. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00273g

2JHH-resolved HSQC: Exclusive determination of geminal proton-proton coupling constants

NASA Astrophysics Data System (ADS)

Marcó, Núria; Nolis, Pau; Gil, Roberto R.; Parella, Teodor

2017-09-01

The measurement of two-bond proton-proton coupling constants (2JHH) in prochiral CH2 groups from the F2 dimension of 2D spectra is not easy due to the usual presence of complex multiplet J patterns, line broadening effects and strong coupling artifacts. These drawbacks are particularly pronounced and frequent in AB spin systems, as those normally exhibited by the pair of diastereotopic CH2 protons. Here, a novel 2JHH-resolved HSQC experiment for the exclusive and accurate determination of the magnitude of 2JHH from the doublet displayed along the highly-resolved indirect F1 dimension is described. A pragmatic 2JHH NMR profile affords a fast overview of the full range of existing 2JHH values. In addition, a 2JHH/δ(13C)-scaled version proves to be an efficient solution when severe signal overlapping complicate a rigorous analysis. The performance of the method is compared with other current techniques and illustrated by the determination of challenging residual dipolar 2DHH coupling constants of small molecules dissolved in weakly orienting media.

First-order dipolar phase transition in the Dicke model with infinitely coordinated frustrating interaction

NASA Astrophysics Data System (ADS)

Mukhin, S. I.; Gnezdilov, N. V.

2018-05-01

We found analytically a first-order quantum phase transition in a Cooper pair box array of N low-capacitance Josephson junctions capacitively coupled to resonant photons in a microwave cavity. The Hamiltonian of the system maps on the extended Dicke Hamiltonian of N spins 1 /2 with infinitely coordinated antiferromagnetic (frustrating) interaction. This interaction arises from the gauge-invariant coupling of the Josephson-junction phases to the vector potential of the resonant photons field. In the N ≫1 semiclassical limit, we found a critical coupling at which the ground state of the system switches to one with a net collective electric dipole moment of the Cooper pair boxes coupled to a super-radiant equilibrium photonic condensate. This phase transition changes from the first to second order if the frustrating interaction is switched off. A self-consistently "rotating" Holstein-Primakoff representation for the Cartesian components of the total superspin is proposed, that enables one to trace both the first- and the second-order quantum phase transitions in the extended and standard Dicke models, respectively.

Bound and resonance states of the dipolar anion of hydrogen cyanide: Competition between threshold effects and rotation in an open quantum system

DOE PAGES

Fossez, K.; Michel, N.; Nazarewicz, W.; ...

2015-01-12

In this paper, bound and resonance states of the dipole-bound anion of hydrogen cyanide HCN – are studied using a nonadiabatic pseudopotential method and the Berggren expansion technique involving bound states, decaying resonant states, and nonresonant scattering continuum. We devise an algorithm to identify the resonant states in the complex energy plane. To characterize spatial distributions of electronic wave functions, we introduce the body-fixed density and use it to assign families of resonant states into collective rotational bands. We find that the nonadiabatic coupling of electronic motion to molecular rotation results in a transition from the strong-coupling to weak-coupling regime.more » In the strong-coupling limit, the electron moving in a subthreshold, spatially extended halo state follows the rotational motion of the molecule. Above the ionization threshold, the electron's motion in a resonance state becomes largely decoupled from molecular rotation. Finally, the widths of resonance-band members depend primarily on the electron orbital angular momentum.« less

Electrostatic contribution to the persistence length of a semiflexible dipolar chain.

PubMed

Podgornik, Rudi

2004-09-01

We investigate the electrostatic contribution to the persistence length of a semiflexible polymer chain whose segments interact via a screened Debye-Hückel dipolar interaction potential. We derive the expressions for the renormalized persistence length on the level of a 1/D-expansion method already successfully used in other contexts of polyelectrolye physics. We investigate different limiting forms of the renormalized persistence length of the dipolar chain and show that, in, general, it depends less strongly on the screening length than in the context of a monopolar chain. We show that for a dipolar chain the electrostatic persistence length in the same regime of the parameter phase space as the original Odijk-Skolnick-Fixman (OSF) form for a monopolar chain depends logarithmically on the screening length rather than quadratically. This can be understood solely on the basis of a swifter decay of the dipolar interactions with separation compared to the monopolar electrostatic interactions. We comment also on the general contribution of higher multipoles to the electrostatic renormalization of the bending rigidity.

Internal structure of vortices in a dipolar spinor Bose-Einstein condensate

NASA Astrophysics Data System (ADS)

Borgh, Magnus O.; Lovegrove, Justin; Ruostekoski, Janne

2017-04-01

We demonstrate how dipolar interactions (DI) can have pronounced effects on the structure of vortices in atomic spinor Bose-Einstein condensates and illustrate generic physical principles that apply across dipolar spinor systems. We then find and analyze the cores of singular non-Abelian vortices in a spin-3 52Cr condensate. Using a simpler spin-1 model system, we analyze the underlying dipolar physics and show how a dipolar healing length interacts with the hierarchy of healing lengths of the contact interaction and leads to simple criteria for the core structure: vortex core size is restricted to the shorter spin-dependent healing length when the interactions both favor the ground-state spin condition, but can conversely be enlarged by DI when interactions compete. We further demonstrate manifestations of spin-ordering induced by the DI anisotropy, including DI-dependent angular momentum of nonsingular vortices, as a result of competition with adaptation to rotation, and potentially observable internal vortex-core spin textures. We acknowledge financial support from the EPSRC.

Ferrotoroidic ground state in a heterometallic {CrIIIDyIII6} complex displaying slow magnetic relaxation.

PubMed

Vignesh, Kuduva R; Soncini, Alessandro; Langley, Stuart K; Wernsdorfer, Wolfgang; Murray, Keith S; Rajaraman, Gopalan

2017-10-18

Toroidal quantum states are most promising for building quantum computing and information storage devices, as they are insensitive to homogeneous magnetic fields, but interact with charge and spin currents, allowing this moment to be manipulated purely by electrical means. Coupling molecular toroids into larger toroidal moments via ferrotoroidic interactions can be pivotal not only to enhance ground state toroidicity, but also to develop materials displaying ferrotoroidic ordered phases, which sustain linear magneto-electric coupling and multiferroic behavior. However, engineering ferrotoroidic coupling is known to be a challenging task. Here we have isolated a {Cr III Dy III 6 } complex that exhibits the much sought-after ferrotoroidic ground state with an enhanced toroidal moment, solely arising from intramolecular dipolar interactions. Moreover, a theoretical analysis of the observed sub-Kelvin zero-field hysteretic spin dynamics of {Cr III Dy III 6 } reveals the pivotal role played by ferrotoroidic states in slowing down the magnetic relaxation, in spite of large calculated single-ion quantum tunneling rates.

Velocity Enhancement by Synchronization of Magnetic Domain Walls

NASA Astrophysics Data System (ADS)

Hrabec, Aleš; Křižáková, Viola; Pizzini, Stefania; Sampaio, João; Thiaville, André; Rohart, Stanislas; Vogel, Jan

2018-06-01

Magnetic domain walls are objects whose dynamics is inseparably connected to their structure. In this Letter, we investigate magnetic bilayers, which are engineered such that a coupled pair of domain walls, one in each layer, is stabilized by a cooperation of Dzyaloshinskii-Moriya interaction and flux-closing mechanism. The dipolar field mediating the interaction between the two domain walls links not only their position but also their structure. We show that this link has a direct impact on their magnetic-field-induced dynamics. We demonstrate that in such a system the coupling leads to an increased domain wall velocity with respect to single domain walls. Since the domain wall dynamics is observed in a precessional regime, the dynamics involves the synchronization between the two walls to preserve the flux closure during motion. Properties of these coupled oscillating walls can be tuned by an additional in-plane magnetic field enabling a rich variety of states, from perfect synchronization to complete detuning.

Cycloadditions in modern polymer chemistry.

PubMed

Delaittre, Guillaume; Guimard, Nathalie K; Barner-Kowollik, Christopher

2015-05-19

Synthetic polymer chemistry has undergone two major developments in the last two decades. About 20 years ago, reversible-deactivation radical polymerization processes started to give access to a wide range of polymeric architectures made from an almost infinite reservoir of functional building blocks. A few years later, the concept of click chemistry revolutionized the way polymer chemists approached synthetic routes. Among the few reactions that could qualify as click, the copper-catalyzed azide-alkyne cycloaddition (CuAAC) initially stood out. Soon, many old and new reactions, including cycloadditions, would further enrich the synthetic macromolecular chemistry toolbox. Whether click or not, cycloadditions are in any case powerful tools for designing polymeric materials in a modular fashion, with a high level of functionality and, sometimes, responsiveness. Here, we wish to describe cycloaddition methodologies that have been reported in the last 10 years in the context of macromolecular engineering, with a focus on those developed in our laboratories. The overarching structure of this Account is based on the three most commonly encountered cycloaddition subclasses in organic and macromolecular chemistry: 1,3-dipolar cycloadditions, (hetero-)Diels-Alder cycloadditions ((H)DAC), and [2+2] cycloadditions. Our goal is to briefly describe the relevant reaction conditions, the advantages and disadvantages, and the realized polymer applications. Furthermore, the orthogonality of most of these reactions is highlighted because it has proven highly beneficial for generating unique, multifunctional polymers in a one-pot reaction. The overview on 1,3-dipolar cycloadditions is mostly centered on the application of CuAAC as the most travelled route, by far. Besides illustrating the capacity of CuAAC to generate complex polymeric architectures, alternative 1,3-dipolar cycloadditions operating without the need for a catalyst are described. In the area of (H)DA cycloadditions, beyond the popular maleimide/furan couple, we present chemistries based on more reactive species, such as cyclopentadienyl or thiocarbonylthio moieties, particularly stressing the reversibility of these systems. In these two greater families, as well as in the last section on [2+2] cycloadditions, we highlight phototriggered chemistries as a powerful tool for spatially and temporally controlled materials synthesis. Clearly, cycloaddition chemistry already has and will continue to transform the field of polymer chemistry in the years to come. Applying this chemistry enables better control over polymer composition, the development of more complicated polymer architectures, the simplification of polymer library production, and the discovery of novel applications for all of these new polymers.

Energetic electron acceleration and injection during dipolarization events in Mercury's magnetotail

NASA Astrophysics Data System (ADS)

Dewey, R. M.; Slavin, J. A.; Raines, J. M.; Baker, D. N.; Lawrence, D. J.

2017-12-01

MESSENGER frequently observed bursts of energetic electrons (>10 keV to 300 keV) within Mercury's miniature terrestrial-like magnetosphere. These bursts are observed most often in the post-midnight sector near the magnetic equator, suggestive of the acceleration and injection of electrons from the magnetotail and their eastward drift about the planet. We use the Gamma-Ray Spectrometer's high-time resolution (10 ms) energetic electron measurements to examine the relationship between energetic electron injections and magnetospheric dynamics in Mercury's magnetotail. We find that these electron injections were observed most frequently in association with magnetic field dipolarization. Between March 2013 and April 2015, we identified 2976 magnetotail electron events of which 538 were coincident with the leading edge of a dipolarization event. These dipolarization fronts were detected on the basis of their rapid ( 2 s) increase in the northward component of the tail magnetic field (ΔBz 30 nT), which typically persists for 10 s. We find electrons experience brief, yet intense, betatron and Fermi acceleration during these dipolarization events, reaching energies 160 keV and contributing to nightside precipitation. Dipolarization events, and subsequently, the electron acceleration associated with them, display a strong dawn-dusk asymmetry, suggestive of a post-midnight maximum in magnetotail reconnection.

Bias-free spin-wave phase shifter for magnonic logic

DOE Office of Scientific and Technical Information (OSTI.GOV)

Louis, Steven; Tyberkevych, Vasyl; Slavin, Andrei

2016-06-15

A design of a magnonic phase shifter operating without an external bias magnetic field is proposed. The phase shifter uses a localized collective spin wave mode propagating along a domain wall “waveguide” in a dipolarly-coupled magnetic dot array with a chessboard antiferromagnetic (CAFM) ground state. It is demonstrated numerically that the remagnetization of a single magnetic dot adjacent to the domain wall waveguide introduces a controllable phase shift in the propagating spin wave mode without significant change to the mode amplitude. It is also demonstrated that a logic XOR gate can be realized in the same system.

Direct measurement of magnon temperature: new insight into magnon-phonon coupling in magnetic insulators.

PubMed

Agrawal, M; Vasyuchka, V I; Serga, A A; Karenowska, A D; Melkov, G A; Hillebrands, B

2013-09-06

We present spatially resolved measurements of the magnon temperature in a magnetic insulator subject to a thermal gradient. Our data reveal an unexpectedly close correspondence between the spatial dependencies of the exchange magnon and phonon temperatures. These results indicate that if--as is currently thought--the transverse spin Seebeck effect is caused by a temperature difference between the magnon and phonon baths, it must be the case that the magnon temperature is spectrally nonuniform and that the effect is driven by the sparsely populated dipolar region of the magnon spectrum.

Rydberg Excitation of a Single Trapped Ion.

PubMed

Feldker, T; Bachor, P; Stappel, M; Kolbe, D; Gerritsma, R; Walz, J; Schmidt-Kaler, F

2015-10-23

We demonstrate excitation of a single trapped cold (40)Ca(+) ion to Rydberg levels by laser radiation in the vacuum ultraviolet at a wavelength of 122 nm. Observed resonances are identified as 3d(2)D(3/2) to 51F, 52F and 3d(2)D(5/2) to 64F. We model the line shape and our results imply a large state-dependent coupling to the trapping potential. Rydberg ions are of great interest for future applications in quantum computing and simulation, in which large dipolar interactions are combined with the superb experimental control offered by Paul traps.

Ion Transport and Acceleration at Dipolarization Fronts: High-Resolution MHD/Test-Particle Simulations

NASA Astrophysics Data System (ADS)

Ukhorskiy, A. Y.; Sorathia, K.; Merkin, V. G.; Sitnov, M. I.; Mitchell, D. G.; Wiltberger, M. J.; Lyon, J.

2017-12-01

Much of plasma heating and transport from the magnetotail into the inner magnetosphere occurs in the form of mesoscale discrete injections associated with sharp dipolarizations of magnetic field (dipolarization fronts). In this study we investigate the mechanisms of ion acceleration at dipolarization fronts in a high-resolution global magnetospheric MHD model (LFM). We use large-scale three-dimensional test-particle simulations (CHIMP) to address the following science questions: 1) what are the characteristic scales of dipolarization regions that can stably trap ions? 2) what role does the trapping play in ion transport and acceleration? 3) how does it depend on particle energy and distance from Earth? 4) to what extent ion acceleration is adiabatic? High-resolution LFM was run using idealized solar wind conditions with fixed nominal values of density and velocity and a southward IMF component of -5 nT. To simulate ion interaction with dipolarization fronts, a large ensemble of test particles distributed in energy, pitch-angle, and gyrophase was initialized inside one of the LFM dipolarization channels in the magnetotail. Full Lorentz ion trajectories were then computed over the course of the front inward propagation from the distance of 17 to 6 Earth radii. A large fraction of ions with different initial energies stayed in phase with the front over the entire distance. The effect of magnetic trapping at different energies was elucidated with a correlation of the ion guiding center and the ExB drift velocities. The role of trapping in ion energization was quantified by comparing the partial pressure of ions that exhibit trapping to the pressure of all trapped ions.

Homonuclear Hartmann-Hahn transfer with reduced relaxation losses by use of the MOCCA-XY16 multiple pulse sequence

NASA Astrophysics Data System (ADS)

Furrer, Julien; Kramer, Frank; Marino, John P.; Glaser, Steffen J.; Luy, Burkhard

2004-01-01

Homonuclear Hartmann-Hahn transfer is one of the most important building blocks in modern high-resolution NMR. It constitutes a very efficient transfer element for the assignment of proteins, nucleic acids, and oligosaccharides. Nevertheless, in macromolecules exceeding ˜10 kDa TOCSY-experiments can show decreasing sensitivity due to fast transverse relaxation processes that are active during the mixing periods. In this article we propose the MOCCA-XY16 multiple pulse sequence, originally developed for efficient TOCSY transfer through residual dipolar couplings, as a homonuclear Hartmann-Hahn sequence with improved relaxation properties. A theoretical analysis of the coherence transfer via scalar couplings and its relaxation behavior as well as experimental transfer curves for MOCCA-XY16 relative to the well-characterized DIPSI-2 multiple pulse sequence are given.

Homonuclear Hartmann-Hahn transfer with reduced relaxation losses by use of the MOCCA-XY16 multiple pulse sequence.

PubMed

Furrer, Julien; Kramer, Frank; Marino, John P; Glaser, Steffen J; Luy, Burkhard

2004-01-01

Homonuclear Hartmann-Hahn transfer is one of the most important building blocks in modern high-resolution NMR. It constitutes a very efficient transfer element for the assignment of proteins, nucleic acids, and oligosaccharides. Nevertheless, in macromolecules exceeding approximately 10 kDa TOCSY-experiments can show decreasing sensitivity due to fast transverse relaxation processes that are active during the mixing periods. In this article we propose the MOCCA-XY16 multiple pulse sequence, originally developed for efficient TOCSY transfer through residual dipolar couplings, as a homonuclear Hartmann-Hahn sequence with improved relaxation properties. A theoretical analysis of the coherence transfer via scalar couplings and its relaxation behavior as well as experimental transfer curves for MOCCA-XY16 relative to the well-characterized DIPSI-2 multiple pulse sequence are given.

Interplay Between Hydrophobic Effect and Dipole Interactions in Peptide Aggregation

NASA Astrophysics Data System (ADS)

Ganesan, Sai; Matysiak, Silvina

In the past decade, the development of various coarse-grained models for proteins have provided key insights into the driving forces in folding and aggregation.We recently developed a low resolution Water Explicit Polarizable PROtein coarse-grained Model by adding oppositely charged dummy particles inside protein backbone beads.With this model,we were able to achieve significant α/ β secondary structure content,without any added bias.We now extend the model to study peptide aggregation at hydrophobic-hydrophilic interface using elastin-like octapeptides (GV)4 as a model system.A condensation-ordering mechanism of aggregation is observed in water.Our results suggest that backbone interpeptide dipolar interactions,not hydrophobicity,plays a more significant role in fibril-like peptide aggregation.We observe a cooperative effect in hydrogen bonding or dipolar interactions, with increase in aggregate size in water and interface.Based on this cooperative effect, we provide a potential explanation for the observed nucleus size in peptide aggregation pathways.Without dipolar particles,peptide aggregation is not observed at the hydrophilic-hydrophobic interface.Thus,the presence of dipoles,not hydrophobicity plays a key role in aggregation observed at hydrophobic interfaces.

Weaker axially dipolar time-averaged paleomagnetic field based on multidomain-corrected paleointensities from Galapagos lavas.

PubMed

Wang, Huapei; Kent, Dennis V; Rochette, Pierre

2015-12-08

The geomagnetic field is predominantly dipolar today, and high-fidelity paleomagnetic mean directions from all over the globe strongly support the geocentric axial dipole (GAD) hypothesis for the past few million years. However, the bulk of paleointensity data fails to coincide with the axial dipole prediction of a factor-of-2 equator-to-pole increase in mean field strength, leaving the core dynamo process an enigma. Here, we obtain a multidomain-corrected Pliocene-Pleistocene average paleointensity of 21.6 ± 11.0 µT recorded by 27 lava flows from the Galapagos Archipelago near the Equator. Our new result in conjunction with a published comprehensive study of single-domain-behaved paleointensities from Antarctica (33.4 ± 13.9 µT) that also correspond to GAD directions suggests that the overall average paleomagnetic field over the past few million years has indeed been dominantly dipolar in intensity yet only ∼ 60% of the present-day field strength, with a long-term average virtual axial dipole magnetic moment of the Earth of only 4.9 ± 2.4 × 10(22) A ⋅ m(2).

Weaker axially dipolar time-averaged paleomagnetic field based on multidomain-corrected paleointensities from Galapagos lavas

PubMed Central

Wang, Huapei; Kent, Dennis V.; Rochette, Pierre

2015-01-01

The geomagnetic field is predominantly dipolar today, and high-fidelity paleomagnetic mean directions from all over the globe strongly support the geocentric axial dipole (GAD) hypothesis for the past few million years. However, the bulk of paleointensity data fails to coincide with the axial dipole prediction of a factor-of-2 equator-to-pole increase in mean field strength, leaving the core dynamo process an enigma. Here, we obtain a multidomain-corrected Pliocene–Pleistocene average paleointensity of 21.6 ± 11.0 µT recorded by 27 lava flows from the Galapagos Archipelago near the Equator. Our new result in conjunction with a published comprehensive study of single-domain–behaved paleointensities from Antarctica (33.4 ± 13.9 µT) that also correspond to GAD directions suggests that the overall average paleomagnetic field over the past few million years has indeed been dominantly dipolar in intensity yet only ∼60% of the present-day field strength, with a long-term average virtual axial dipole magnetic moment of the Earth of only 4.9 ± 2.4 × 1022 A⋅m2. PMID:26598664

Quasi-parallel whistler mode waves observed by THEMIS during near-earth dipolarizations

NASA Astrophysics Data System (ADS)

Le Contel, O.; Roux, A.; Jacquey, C.; Robert, P.; Berthomier, M.; Chust, T.; Grison, B.; Angelopoulos, V.; Sibeck, D.; Chaston, C. C.; Cully, C. M.; Ergun, B.; Glassmeier, K.-H.; Auster, U.; McFadden, J.; Carlson, C.; Larson, D.; Bonnell, J. W.; Mende, S.; Russell, C. T.; Donovan, E.; Mann, I.; Singer, H.

2009-06-01

We report on quasi-parallel whistler emissions detected by the near-earth satellites of the THEMIS mission before, during, and after local dipolarization. These emissions are associated with an electron temperature anisotropy α=T⊥e/T||e>1 consistent with the linear theory of whistler mode anisotropy instability. When the whistler mode emissions are observed the measured electron anisotropy varies inversely with β||e (the ratio of the electron parallel pressure to the magnetic pressure) as predicted by Gary and Wang (1996). Narrow band whistler emissions correspond to the small α existing before dipolarization whereas the broad band emissions correspond to large α observed during and after dipolarization. The energy in the whistler mode is leaving the current sheet and is propagating along the background magnetic field, towards the Earth. A simple time-independent description based on the Liouville's theorem indicates that the electron temperature anisotropy decreases with the distance along the magnetic field from the equator. Once this variation of α is taken into account, the linear theory predicts an equatorial origin for the whistler mode. The linear theory is also consistent with the observed bandwidth of wave emissions. Yet, the anisotropy required to be fully consistent with the observations is somewhat larger than the measured one. Although the discrepancy remains within the instrumental error bars, this could be due to time-dependent effects which have been neglected. The possible role of the whistler waves in the substorm process is discussed.

Adimensional theory of shielding in ultracold collisions of dipolar rotors

NASA Astrophysics Data System (ADS)

González-Martínez, Maykel L.; Bohn, John L.; Quéméner, Goulven

2017-09-01

We investigate the electric field shielding of ultracold collisions of dipolar rotors, initially in their first rotational excited state, using an adimensional approach. We establish a map of good and bad candidates for efficient evaporative cooling based on this shielding mechanism, by presenting the ratio of elastic over quenching processes as a function of a rescaled rotational constant B ˜=B /sE3 and a rescaled electric field F ˜=d F /B . B ,d ,F ,andsE 3 are respectively the rotational constant, the full electric dipole moment of the molecules, the applied electric field, and a characteristic dipole-dipole energy. We identify two groups of bi-alkali-metal dipolar molecules. The first group, including RbCs, NaK, KCs, LiK, NaRb, LiRb, NaCs, and LiCs, is favorable with a ratio over 1000 at collision energies equal to (or even higher than) their characteristic dipolar energy. The second group, including LiNa and KRb, is not favorable. More generally, for molecules well described by Hund's case b, our adimensional study provides the conditions of efficient evaporative cooling. The range of appropriate rescaled rotational constant and rescaled field is approximately B ˜≥108 and 3.25 ≤F ˜≤3.8 , with a maximum ratio reached for F ˜≃3.4 for a given B ˜. We also discuss the importance of the electronic van der Waals interaction on the adimensional character of our study.

Isospin equilibration processes and dipolar signals: Coherent cluster production

NASA Astrophysics Data System (ADS)

Papa, M.; Berceanu, I.; Acosta, L.; Agodi, C.; Auditore, L.; Cardella, G.; Chatterjee, M. B.; Dell'Aquila, D.; De Filippo, E.; Francalanza, L.; Lanzalone, G.; Lombardo, I.; Maiolino, C.; Martorana, N.; Pagano, A.; Pagano, E. V.; Pirrone, S.; Politi, G.; Quattrocchi, L.; Rizzo, F.; Russotto, P.; Trifiró, A.; Trimarchi, M.; Verde, G.; Vigilante, M.

2017-11-01

The total dipolar signal related to multi-break-up processes induced on the system ^{48}Ca +{^{27}Al} at 40MeV/nucleon has been investigated with the CHIMERA multi-detector. Experimental data related to semi-peripheral collisions are shown and compared with CoMD-III calculations. The strong connection between the dipolar signal as obtained from the detected fragments and the dynamics of the isospin equilibration processes is also shortly discussed.

Third-harmonic generation from Mie-type resonances of isolated all-dielectric nanoparticles

NASA Astrophysics Data System (ADS)

Melik-Gaykazyan, Elizaveta V.; Shcherbakov, Maxim R.; Shorokhov, Alexander S.; Staude, Isabelle; Brener, Igal; Neshev, Dragomir N.; Kivshar, Yuri S.; Fedyanin, Andrey A.

2017-03-01

Subwavelength silicon nanoparticles are known to support strongly localized Mie-type modes, including those with resonant electric and magnetic dipolar polarizabilities. Here we compare experimentally the efficiency of the third-harmonic generation from isolated silicon nanodiscs for resonant excitation at the two types of dipolar resonances. Using nonlinear spectroscopy, we observe that the magnetic dipolar mode yields more efficient third-harmonic radiation in contrast to the electric dipolar (ED) mode. This is further supported by full-wave numerical simulations, where the volume-integrated local fields and the directly simulated nonlinear response are shown to be negligible at the ED resonance compared with the magnetic one. This article is part of the themed issue 'New horizons for nanophotonics'.

Dipolar sources of the early scalp somatosensory evoked potentials to upper limb stimulation. Effect of increasing stimulus rates.

PubMed

Valeriani, M; Restuccia, D; Di Lazzaro, V; Le Pera, D; Barba, C; Tonali, P; Mauguiere, F

1998-06-01

Brain electrical source analysis (BESA) of the scalp electroencephalographic activity is well adapted to distinguish neighbouring cerebral generators precisely. Therefore, we performed dipolar source modelling in scalp medium nerve somatosensory evoked potentials (SEPs) recorded at 1.5-Hz stimulation rate, where all the early components should be identifiable. We built a four-dipole model, which was issued from the grand average, and applied it also to recordings from single individuals. Our model included a dipole at the base of the skull and three other perirolandic dipoles. The first of the latter dipoles was tangentially oriented and was active at the same latencies as the N20/P20 potential and, with opposite polarity, the P24/N24 response. The second perirolandic dipole showed an initial peak of activity slightly earlier than that of the N20/P20 dipolar source and, later, it was active at the same latency as the central P22 potential. Lastly, the third perirolandic dipole explaining the fronto-central N30 potential scalp distribution was constantly more posterior than the first one. In order to evaluate the effect of an increasing repetition frequency on the activity of SEP dipolar sources, we applied the model built from 1.5-Hz SEPs to traces recorded at 3-Hz and 10-Hz repetition rates. We found that the 10-Hz stimulus frequency reduced selectively the later of the two activity phases of the first perirolandic dipole. The decrement in strength of this dipolar source can be explained if we assume that: (a) the later activity of the first perirolandic dipole can represent the inhibitory phase of a "primary response"; (b) two different clusters of cells generate the opposite activities of the tangential perirolandic dipole. An additional finding in our model was that two different perirolandic dipoles contribute to the centro-parietal N20 potential generation.

Pitch angle distributions of electrons at dipolarization sites during geomagnetic activity: THEMIS observations

NASA Astrophysics Data System (ADS)

Wang, Kaiti; Lin, Ching-Huei; Wang, Lu-Yin; Hada, Tohru; Nishimura, Yukitoshi; Turner, Drew L.; Angelopoulos, Vassilis

2014-12-01

Changes in pitch angle distributions of electrons with energies from a few eV to 1 MeV at dipolarization sites in Earth's magnetotail are investigated statistically to determine the extent to which adiabatic acceleration may contribute to these changes. Forty-two dipolarization events from 2008 and 2009 observed by Time History of Events and Macroscale Interactions during Substorms probes covering the inner plasma sheet from 8 RE to 12 RE during geomagnetic activity identified by the AL index are analyzed. The number of observed events with cigar-type distributions (peaks at 0° and 180°) decreases sharply below 1 keV after dipolarization because in many of these events, electron distributions became more isotropized. From above 1 keV to a few tens of keV, however, the observed number of cigar-type events increases after dipolarization and the number of isotropic events decreases. These changes can be related to the ineffectiveness of Fermi acceleration below 1 keV (at those energies, dipolarization time becomes comparable to electron bounce time). Model-calculated pitch angle distributions after dipolarization with the effect of betatron and Fermi acceleration tested indicate that these adiabatic acceleration mechanisms can explain the observed patterns of event number changes over a large range of energies for cigar events and isotropic events. Other factors still need to be considered to assess the observed increase in cigar events around 2 keV. Indeed, preferential directional increase/loss of electron fluxes, which may contribute to the formation of cigar events, was observed. Nonadiabatic processes to accelerate electrons in a parallel direction may also be important for future study.

Solution Structure of the 128 kDa Enzyme I Dimer from Escherichia coli and Its 146 kDa Complex with HPr Using Residual Dipolar Couplings and Small- and Wide-Angle X-ray Scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwieters, Charles D.; Suh, Jeong-Yong; Grishaev, Alexander

2010-09-17

The solution structures of free Enzyme I (EI, {approx}128 kDa, 575 x 2 residues), the first enzyme in the bacterial phosphotransferase system, and its complex with HPr ({approx}146 kDa) have been solved using novel methodology that makes use of prior structural knowledge (namely, the structures of the dimeric EIC domain and the isolated EIN domain both free and complexed to HPr), combined with residual dipolar coupling (RDC), small- (SAXS) and wide- (WAXS) angle X-ray scattering and small-angle neutron scattering (SANS) data. The calculational strategy employs conjoined rigid body/torsion/Cartesian simulated annealing, and incorporates improvements in calculating and refining against SAXS/WAXS datamore » that take into account complex molecular shapes in the description of the solvent layer resulting in a better representation of the SAXS/WAXS data. The RDC data orient the symmetrically related EIN domains relative to the C{sub 2} symmetry axis of the EIC dimer, while translational, shape, and size information is provided by SAXS/WAXS. The resulting structures are independently validated by SANS. Comparison of the structures of the free EI and the EI-HPr complex with that of the crystal structure of a trapped phosphorylated EI intermediate reveals large ({approx}70-90{sup o}) hinge body rotations of the two subdomains comprising the EIN domain, as well as of the EIN domain relative to the dimeric EIC domain. These large-scale interdomain motions shed light on the structural transitions that accompany the catalytic cycle of EI.« less

Intermolecular interactions between imidazole derivatives intercalated in layered solids. Substituent group effect

DOE Office of Scientific and Technical Information (OSTI.GOV)

González, M.; Lemus-Santana, A.A.; Rodríguez-Hernández, J.

2013-08-15

This study sheds light on the intermolecular interactions between imidazole derive molecules (2-methyl-imidazole, 2-ethyl-imidazole and benzimidazole) intercalated in T[Ni(CN){sub 4}] layers to form a solid of formula unit T(ImD){sub 2}[Ni(CN){sub 4}]. These hybrid inorganic–organic solids were prepared by soft chemical routes and their crystal structures solved and refined from X-ray powder diffraction data. The involved imidazole derivative molecules were found coordinated through the pyridinic N atom to the axial positions for the metal T in the T[Ni(CN){sub 4}] layer. In the interlayers region ligand molecules from neighboring layers remain stacked in a face-to-face configuration through dipole–dipole and quadrupole–quadrupole interactions. Thesemore » intermolecular interactions show a pronounced dependence on the substituent group and are responsible for an ImD-pillaring concatenation of adjacent layers. This is supported by the structural information and the recorded magnetic data in the 2–300 K temperature range. The samples containing Co and Ni are characterized by presence of spin–orbit coupling and pronounced temperature dependence for the effective magnetic moment except for 2-ethyl-imidazole related to the local distortion for the metal coordination environment. For this last one ligand a weak ferromagnetic ordering ascribed to a super-exchange interaction between T metals from neighboring layers through the ligands π–π interaction was detected. - Graphical abstract: In the interlayers region imidazole derivative molecules are oriented according to their dipolar and quadrupolar interactions and minimizing the steric impediment. Highlights: • Imidazole derivatives intercalation compounds. • Intermolecular interaction between intercalated imidazole derivatives. • Hybrid inorganic–organic solids. • Pi–pi interactions and ferromagnetic coupling. • Dipolar and quadrupolar interactions between intercalated imidazole derivatives.« less

Observing the Plasma-Physical Processes of Pulsar Radio Emission with Arecibo

NASA Astrophysics Data System (ADS)

Rankin, Joanna M.

2017-01-01

With their enormous densities and fields, neutron stars entail some of the most exotic physics in the cosmos. Similarly, the physical mechanisms of pulsar radio emission are no less exotic, and we are only now beginning to understand them. The talk will provide an introduction to the phenomenology of radio pulsar emission and focus on those aspects of the exquisite Arecibo observations that bear on their challenging emission physics.The commonalities of the radio beamforms of most slow pulsars (and some millisecond pulsars) argue strongly that their magnetic fields have a nearly dipolar structure at the height of their radio emission regions. These heights can often be determined by aberration/retardation analyses. Similarly, measurement of the orientation of the polarized radio emission with respect to the emitting magnetic field facilitates identification of the physical(X/O) emission modes and study of the plasma coupling to the electromagnetic radiation.While the physics of primary plasma generation above the pulsar polar cap is only beginning to be understood, it is clear that the radio pulsars we see are able to generate copious amounts of electron-positron plasma in their emission regions. Within the nearly dipolar field structure of these emission regions, the plasma density is near to that of the Goldreich-Julian model, and so the physical conditions in these regions can be accurately estimated.These conditions show that the plasma frequencies in the emission regions are much higher than the frequency of the emitted radiation, such that the plasma couples most easily to the extraordinary mode as observed. Therefore, the only surviving emission mechanism is curvature radiation from charged solitons, produced by the two-stream instability. Such soliton emission has probably been observed directly in the Crab pulsar; however, a physical theory of charged soliton radiation does not yet exist.

Adaptation of a 3-D Quadrupole Ion Trap for Dipolar DC Collisional Activation

PubMed Central

Prentice, Boone M.; Santini, Robert E.; McLuckey, Scott A.

2011-01-01

Means to allow for the application of a dipolar DC pulse to the end-cap electrodes of a three-dimensional (3-D) quadrupole ion trap for as short as a millisecond to as long as hundreds of milliseconds are described. The implementation of dipolar DC does not compromise the ability to apply AC waveforms to the end-cap electrodes at other times in the experiment. Dipolar DC provides a nonresonant means for ion acceleration by displacing ions from the center of the ion trap where they experience stronger rf electric fields, which increases the extent of micro-motion. The evolution of the product ion spectrum to higher generation products with time, as shown using protonated leucine enkephalin as a model protonated peptide, illustrates the broad-band nature of the activation. Dipolar DC activation is also shown to be effective as an ion heating approach in mimicking high amplitude short time excitation (HASTE)/pulsed Q dissociation (PQD) resonance excitation experiments that are intended to enhance the likelihood for observing low m/z products in ion trap tandem mass spectrometry. PMID:21953251

Pressure and compressibility factor of bidisperse magnetic fluids

NASA Astrophysics Data System (ADS)

Minina, Elena S.; Blaak, Ronald; Kantorovich, Sofia S.

2018-04-01

In this work, we investigate the pressure and compressibility factors of bidisperse magnetic fluids with relatively weak dipolar interactions and different granulometric compositions. In order to study these properties, we employ the method of diagram expansion, taking into account two possible scenarios: (1) dipolar particles repel each other as hard spheres; (2) the polymer shell on the surface of the particles is modelled through a soft-sphere approximation. The theoretical predictions of the pressure and compressibility factors of bidisperse ferrofluids at different granulometric compositions are supported by data obtained by means of molecular dynamics computer simulations, which we also carried out for these systems. Both theory and simulations reveal that the pressure and compressibility factors decrease with growing dipolar correlations in the system, namely with an increasing fraction of large particles. We also demonstrate that even if dipolar interactions are too weak for any self-assembly to take place, the interparticle correlations lead to a qualitative change in the behaviour of the compressibility factors when compared to that of non-dipolar spheres, making the dependence monotonic.

Scissors Mode of Dipolar Quantum Droplets of Dysprosium Atoms

NASA Astrophysics Data System (ADS)

Ferrier-Barbut, Igor; Wenzel, Matthias; Böttcher, Fabian; Langen, Tim; Isoard, Mathieu; Stringari, Sandro; Pfau, Tilman

2018-04-01

We report on the observation of the scissors mode of a single dipolar quantum droplet. The existence of this mode is due to the breaking of the rotational symmetry by the dipole-dipole interaction, which is fixed along an external homogeneous magnetic field. By modulating the orientation of this magnetic field, we introduce a new spectroscopic technique for studying dipolar quantum droplets. This provides a precise probe for interactions in the system, allowing us to extract a background scattering length for 164Dy of 69 (4 )a0 . Our results establish an analogy between quantum droplets and atomic nuclei, where the existence of the scissors mode is also only due to internal interactions. They further open the possibility to explore physics beyond the available theoretical models for strongly dipolar quantum gases.

Quantum Hall signatures of dipolar Mahan excitons

NASA Astrophysics Data System (ADS)

Schinner, G. J.; Repp, J.; Kowalik-Seidl, K.; Schubert, E.; Stallhofer, M. P.; Rai, A. K.; Reuter, D.; Wieck, A. D.; Govorov, A. O.; Holleitner, A. W.; Kotthaus, J. P.

2013-01-01

We explore the photoluminescence of spatially indirect, dipolar Mahan excitons in a gated double quantum well diode containing a mesoscopic electrostatic trap for neutral dipolar excitons at low temperatures down to 250 mK and in quantizing magnetic fields. Mahan excitons in the surrounding of the trap, consisting of individual holes interacting with a degenerate two-dimensional electron system confined in one of the quantum wells, exhibit strong quantum Hall signatures at integer filling factors and related anomalies around filling factor ν=(2)/(3),(3)/(5), and (1)/(2), reflecting the formation of composite fermions. Interactions across the trap perimeter are found to influence the energy of the confined neutral dipolar excitons by the presence of the quantum Hall effects in the two-dimensional electron system surrounding the trap.

On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin-Spin Coupling Constants

NASA Astrophysics Data System (ADS)

Sanchez, Marina; Provasi, Patricio F.; Aucar, Gustavo A.; Sauer, Stephan P. A.

Locally dense basis sets (

Controlling interactions between highly magnetic atoms with Feshbach resonances.

PubMed

Kotochigova, Svetlana

2014-09-01

This paper reviews current experimental and theoretical progress in the study of dipolar quantum gases of ground and meta-stable atoms with a large magnetic moment. We emphasize the anisotropic nature of Feshbach resonances due to coupling to fast-rotating resonant molecular states in ultracold s-wave collisions between magnetic atoms in external magnetic fields. The dramatic differences in the distribution of resonances of magnetic (7)S3 chromium and magnetic lanthanide atoms with a submerged 4f shell and non-zero electron angular momentum is analyzed. We focus on dysprosium and erbium as important experimental advances have been recently made to cool and create quantum-degenerate gases for these atoms. Finally, we describe progress in locating resonances in collisions of meta-stable magnetic atoms in electronic P-states with ground-state atoms, where an interplay between collisional anisotropies and spin-orbit coupling exists.

Characterization of heteronuclear decoupling through proton spin dynamics in solid-state nuclear magnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

De Paëpe, Gaël; Eléna, Bénédicte; Emsley, Lyndon

2004-08-01

The work presented here aims at understanding the performance of phase modulated heteronuclear decoupling sequences such as Cosine Modulation or Two Pulse Phase Modulation. To that end we provide an analytical description of the intrinsic behavior of Cosine Modulation decoupling with respect to radio-frequency-inhomogeneity and the proton-proton dipolar coupling network. We discover through a Modulation Frame average Hamiltonian analysis that best decoupling is obtained under conditions where the heteronuclear interactions are removed but notably where homonuclear couplings are recoupled at a homonuclear Rotary Resonance (HORROR) condition in the Modulation Frame. These conclusions are supported by extensive experimental investigations, and notably through the introduction of proton nutation experiments to characterize spin dynamics in solids under decoupling conditions. The theoretical framework presented in this paper allows the prediction of the optimum parameters for a given set of experimental conditions.

Local gauge symmetry on optical lattices?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yuzhi; Meurice, Yannick; Tsai, Shan-Wen

2012-11-01

The versatile technology of cold atoms confined in optical lattices allows the creation of a vast number of lattice geometries and interactions, providing a promising platform for emulating various lattice models. This opens the possibility of letting nature take care of sign problems and real time evolution in carefully prepared situations. Up to now, experimentalists have succeeded to implement several types of Hubbard models considered by condensed matter theorists. In this proceeding, we discuss the possibility of extending this effort to lattice gauge theory. We report recent efforts to establish the strong coupling equivalence between the Fermi Hubbard model andmore » SU(2) pure gauge theory in 2+1 dimensions by standard determinantal methods developed by Robert Sugar and collaborators. We discuss the possibility of using dipolar molecules and external fields to build models where the equivalence holds beyond the leading order in the strong coupling expansion.« less

Spin interactions in Graphene-Single Molecule Magnets Hybrids

NASA Astrophysics Data System (ADS)

Cervetti, Christian; Rettori, Angelo; Pini, Maria Gloria; Cornia, Andrea; Repollés, Aña; Luis, Fernando; Rauschenbach, Stephan; Dressel, Martin; Kern, Klaus; Burghard, Marko; Bogani, Lapo

2014-03-01

Graphene is a potential component of novel spintronics devices owing to its long spin diffusion length. Besides its use as spin-transport channel, graphene can be employed for the detection and manipulation of molecular spins. This requires an appropriate coupling between the sheets and the single molecular magnets (SMM). Here, we present a comprehensive characterization of graphene-Fe4 SMM hybrids. The Fe4 clusters are anchored non-covalently to the graphene following a diffusion-limited assembly and can reorganize into random networks when subjected to slightly elevated temperature. Molecules anchored on graphene sheets show unaltered static magnetic properties, whilst the quantum dynamics is profoundly modulated. Interaction with Dirac fermions becomes the dominant spin-relaxation channel, with observable effects produced by graphene phonons and reduced dipolar interactions. Coupling to graphene drives the spins over Villain's threshold, allowing the first observation of strongly-perturbative tunneling processes. Preliminary spin-transport experiments at low-temperature are further presented.

Solid-state NMR adiabatic TOBSY sequences provide enhanced sensitivity for multidimensional high-resolution magic-angle-spinning 1H MR spectroscopy

NASA Astrophysics Data System (ADS)

Andronesi, Ovidiu C.; Mintzopoulos, Dionyssios; Struppe, Jochem; Black, Peter M.; Tzika, A. Aria

2008-08-01

We propose a solid-state NMR method that maximizes the advantages of high-resolution magic-angle-spinning (HRMAS) applied to intact biopsies when compared to more conventional liquid-state NMR approaches. Theoretical treatment, numerical simulations and experimental results on intact human brain biopsies are presented. Experimentally, it is proven that an optimized adiabatic TOBSY (TOtal through Bond correlation SpectroscopY) solid-state NMR pulse sequence for two-dimensional 1H- 1H homonuclear scalar-coupling longitudinal isotropic mixing provides a 20%-50% improvement in signal-to-noise ratio relative to its liquid-state analogue TOCSY (TOtal Correlation SpectroscopY). For this purpose we have refined the C9151 symmetry-based 13C TOBSY pulse sequence for 1H MRS use and compared it to MLEV-16 TOCSY sequence. Both sequences were rotor-synchronized and implemented using WURST-8 adiabatic inversion pulses. As discussed theoretically and shown in simulations, the improved magnetization-transfer comes from actively removing residual dipolar couplings from the average Hamiltonian. Importantly, the solid-state NMR techniques are tailored to perform measurements at low temperatures where sample degradation is reduced. This is the first demonstration of such a concept for HRMAS metabolic profiling of disease processes, including cancer, from biopsies requiring reduced sample degradation for further genomic analysis.

Rational design of dipolar chromophore as an efficient dopant-free hole-transporting material for perovskite solar cells

DOE PAGES

Li, Zhong’an; Zhu, Zonglong; Chueh, Chu -Chen; ...

2016-08-23

In this paper, an electron donor-acceptor (D-A) substituted dipolar chromophore ( BTPA-TCNE) is developed to serve as an efficient dopant-free hole-transporting material (HTM) for perovskite solar cells (PVSCs). BTPA-TCNE is synthesized via a simple reaction between a triphenylamine-based Michler’s base and tetracyanoethylene. This chromophore possesses a zwitterionic resonance structure in the ground state, as evidenced by X-ray crystallography and transient absorption spectroscopies. Moreover, BTPA-TCNE shows an antiparallel molecular packing (i.e., centrosymmetric dimers) in its crystalline state, which cancels out its overall molecular dipole moment to facilitate charge transport. Finally, BTPA-TCNE can be employed as an effective dopant-free HTM to realizemore » an efficient (PCE ≈ 17.0%) PVSC in the conventional n-i-p configuration, outperforming the control device with doped spiro-OMeTAD HTM.« less

Demixing in simple dipolar mixtures: Integral equation versus density functional results

NASA Astrophysics Data System (ADS)

Range, Gabriel M.; Klapp, Sabine H. L.

2004-09-01

Using reference hypernetted chain (RHNC) integral equations and density functional theory in the modified mean-field (MMF) approximation we investigate the phase behavior of binary mixtures of dipolar hard spheres. The two species ( A and B ) differ only in their dipole moments mA and mB , and the central question investigated is under which conditions these asymmetric mixtures can exhibit demixing phase transitions in the fluid phase regime. Results from our two theoretical approaches turn out to strongly differ. Within the RHNC (which we apply to the isotropic high-temperature phase) demixing does indeed occur for dense systems with small interaction parameters Γ=mB2/mA2 . This result generalizes previously reported observations on demixing in mixtures of dipolar and neutral hard spheres (Γ=0) to the case of true dipolar hard sphere mixtures. The RHNC approach also indicates that these demixed fluid phases are isotropic at temperatures accessible by the theory, whereas isotropic-to-ferroelectric transitions occur only at larger Γ . The MMF theory, on the other hand, yields a different picture in which demixing occurs in combination with spontaneous ferroelectricity at all Γ considered. This discrepancy underlines the relevance of correlational effects for the existence of demixing transitions in dipolar systems without dispersive interactions. Indeed, supplementing the dipolar interactions by small, asymmetric amounts of van der Waals-like interactions (and thereby supporting the systems tendency to demix) one finally reaches good agreement between MMF and RHNC results.

Solid-state NMR characterization of cross-linking in EPDM/PP blends from 1H-13C polarization transfer dynamics.

PubMed

Aluas, Mihaela; Filip, Claudiu

2005-05-01

A novel approach for solid-state NMR characterization of cross-linking in polymer blends from the analysis of (1)H-(13)C polarization transfer dynamics is introduced. It extends the model of residual dipolar couplings under permanent cross-linking, typically used to describe (1)H transverse relaxation techniques, by considering a more realistic distribution of the order parameter along a polymer chain in rubbers. Based on a systematic numerical analysis, the extended model was shown to accurately reproduce all the characteristic features of the cross-polarization curves measured on such materials. This is particularly important for investigating blends of great technological potential, like thermoplastic elastomers, where (13)C high-resolution techniques, such as CP-MAS, are indispensable to selectively investigate structural and dynamical properties of the desired component. The validity of the new approach was demonstrated using the example of the CP build-up curves measured on a well resolved EPDM resonance line in a series of EPDM/PP blends.

Nonlocally sensing the magnetic states of nanoscale antiferromagnets with an atomic spin sensor

PubMed Central

Yan, Shichao; Malavolti, Luigi; Burgess, Jacob A. J.; Droghetti, Andrea; Rubio, Angel; Loth, Sebastian

2017-01-01

The ability to sense the magnetic state of individual magnetic nano-objects is a key capability for powerful applications ranging from readout of ultradense magnetic memory to the measurement of spins in complex structures with nanometer precision. Magnetic nano-objects require extremely sensitive sensors and detection methods. We create an atomic spin sensor consisting of three Fe atoms and show that it can detect nanoscale antiferromagnets through minute, surface-mediated magnetic interaction. Coupling, even to an object with no net spin and having vanishing dipolar stray field, modifies the transition matrix element between two spin states of the Fe atom–based spin sensor that changes the sensor’s spin relaxation time. The sensor can detect nanoscale antiferromagnets at up to a 3-nm distance and achieves an energy resolution of 10 μeV, surpassing the thermal limit of conventional scanning probe spectroscopy. This scheme permits simultaneous sensing of multiple antiferromagnets with a single-spin sensor integrated onto the surface. PMID:28560346

High-fidelity spin entanglement using optimal control.

PubMed

Dolde, Florian; Bergholm, Ville; Wang, Ya; Jakobi, Ingmar; Naydenov, Boris; Pezzagna, Sébastien; Meijer, Jan; Jelezko, Fedor; Neumann, Philipp; Schulte-Herbrüggen, Thomas; Biamonte, Jacob; Wrachtrup, Jörg

2014-02-28

Precise control of quantum systems is of fundamental importance in quantum information processing, quantum metrology and high-resolution spectroscopy. When scaling up quantum registers, several challenges arise: individual addressing of qubits while suppressing cross-talk, entangling distant nodes and decoupling unwanted interactions. Here we experimentally demonstrate optimal control of a prototype spin qubit system consisting of two proximal nitrogen-vacancy centres in diamond. Using engineered microwave pulses, we demonstrate single electron spin operations with a fidelity F≈0.99. With additional dynamical decoupling techniques, we further realize high-quality, on-demand entangled states between two electron spins with F>0.82, mostly limited by the coherence time and imperfect initialization. Crosstalk in a crowded spectrum and unwanted dipolar couplings are simultaneously eliminated to a high extent. Finally, by high-fidelity entanglement swapping to nuclear spin quantum memory, we demonstrate nuclear spin entanglement over a length scale of 25 nm. This experiment underlines the importance of optimal control for scalable room temperature spin-based quantum information devices.

Electron-flux infrared response to varying π-bond topology in charged aromatic monomers

PubMed Central

Álvaro Galué, Héctor; Oomens, Jos; Buma, Wybren Jan; Redlich, Britta

2016-01-01

The interaction of delocalized π-electrons with molecular vibrations is key to charge transport processes in π-conjugated organic materials based on aromatic monomers. Yet the role that specific aromatic motifs play on charge transfer is poorly understood. Here we show that the molecular edge topology in charged catacondensed aromatic hydrocarbons influences the Herzberg-Teller coupling of π-electrons with molecular vibrations. To this end, we probe the radical cations of picene and pentacene with benchmark armchair- and zigzag-edges using infrared multiple-photon dissociation action spectroscopy and interpret the recorded spectra via quantum-chemical calculations. We demonstrate that infrared bands preserve information on the dipolar π-electron-flux mode enhancement, which is governed by the dynamical evolution of vibronically mixed and correlated one-electron configuration states. Our results reveal that in picene a stronger charge π-flux is generated than in pentacene, which could justify the differences of electronic properties of armchair- versus zigzag-type families of technologically relevant organic molecules. PMID:27577323

A convergent approach to biocompatible polyglycerol "click" dendrons for the synthesis of modular core-shell architectures and their transport behavior.

PubMed

Wyszogrodzka, Monika; Haag, Rainer

2008-01-01

Dendrimers are an important class of polymeric materials for a broad range of applications in which monodispersity and multivalency are of interest. Here we report on a highly efficient synthetic route towards bifunctional polyglycerol dendrons on a multigram scale. Commercially available triglycerol (1), which is highly biocompatible, was used as starting material. By applying Williamson ether synthesis followed by an ozonolysis/reduction procedure, glycerol-based dendrons up to the fourth generation were prepared. The obtained products have a reactive core, which was further functionalized to the corresponding monoazido derivatives. By applying copper(I)-catalyzed 1,3-dipolar cycloaddition, so-called "click" coupling, a library of core-shell architectures was prepared. After removal of the 1,2-diol protecting groups, water-soluble core-shell architectures 24-27 of different generations were obtained in high yields. In the structure-transport relationship with Nile red we observe a clear dependence on core size and generation of the polyglycerol dendrons.

Weak Long-Range Correlated Motions in a Surface Patch of Ubiquitin Involved in Molecular Recognition

PubMed Central

2011-01-01

Long-range correlated motions in proteins are candidate mechanisms for processes that require information transfer across protein structures, such as allostery and signal transduction. However, the observation of backbone correlations between distant residues has remained elusive, and only local correlations have been revealed using residual dipolar couplings measured by NMR spectroscopy. In this work, we experimentally identified and characterized collective motions spanning four β-strands separated by up to 15 Å in ubiquitin. The observed correlations link molecular recognition sites and result from concerted conformational changes that are in part mediated by the hydrogen-bonding network. PMID:21634390

Quadrupole radiation from terahertz dipole antennas.

PubMed

Rudd, J V; Johnson, J L; Mittleman, D M

2000-10-15

We report what is to our knowledge the first detailed investigation of the polarization state of radiation from lens-coupled terahertz dipole antennas. The radiation exhibits a weak but measurable component that is polarized orthogonally to the orientation of the emitter dipole. The angular radiation pattern of this cross-polarized emission reveals that it is quadrupolar, rather than dipolar, in nature. One can understand this result by taking into account the photocurrent flowing in the strip lines that feed the dipole antenna. A Fresnel-Kirchhoff scalar diffraction calculation is used for calculating the frequency-dependent angular distribution of the radiation pattern, providing satisfactory agreement with the measurements.

Dipolar ordering and glassy freezing in methanol-{beta}-hydroquinone-clathrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woll, H.; Rheinstadter, M. C.; Kruchten, F.

2001-06-01

The dielectric, structural, and thermodynamic properties of single crystals of methanol-{beta}-hydroquinone-clathrates have been studied as function of temperature and of the concentration x of the polar guest molecules. At higher temperatures the dielectric response along the threefold crystal axis is of the quasi-one-dimensional Ising type. At lower temperatures the higher concentrated samples order antiferroelectrically whereas the lower concentrated ones freeze into dipole glasses. The behavior is interpreted in terms of the methanol dipole moments coupled by the electric dipole-dipole interaction which is highly frustrated because of the rhombohedral symmetry of the lattice. The dielectric relaxations have been analyzed.

Catalysis of a 1,3-dipolar reaction by distorted DNA incorporating a heterobimetallic platinum(ii) and copper(ii) complex† †Electronic supplementary information (ESI) available: Experimental details, characterization of cycloadducts and intermediates, computational data. CCDC 1411372 and 1411373. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc02311a

PubMed Central

Rivilla, Iván; de Cózar, Abel; Schäfer, Thomas; Hernandez, Frank J.; Bittner, Alexander M.; Eleta-Lopez, Aitziber; Aboudzadeh, Ali; Santos, José I.; Miranda, José I.

2017-01-01

A novel catalytic system based on covalently modified DNA is described. This catalyst promotes 1,3-dipolar reactions between azomethine ylides and maleimides. The catalytic system is based on the distortion of the double helix of DNA by means of the formation of Pt(ii) adducts with guanine units. This distortion, similar to that generated in the interaction of DNA with platinum chemotherapeutic drugs, generates active sites that can accommodate N-metallated azomethine ylides. The proposed reaction mechanism, based on QM(DFT)/MM calculations, is compatible with thermally allowed concerted (but asynchronous) [π4s + π2s] mechanisms leading to the exclusive formation of racemic endo-cycloadducts. PMID:29147531

An investigation of the structure and bond rotational potential of some fluorinated ethanes by NMR spectroscopy of solutions in nematic liquid crystalline solvents.

PubMed

Emsley, J W; Longeri, M; Merlet, D; Pileio, G; Suryaprakash, N

2006-06-01

NMR spectra of 1,2-dibromo-1,1-difluoroethane and 1-bromo-2-iodo-tetrafluoroethane dissolved in nematic liquid crystalline solvents have been analysed to yield the magnitudes and signs of the scalar couplings, J(ij), and total anisotropic couplings, T(ij), between all the (1)H, (19)F, and (13)C nuclei, except for those between two (13)C nuclei. The values obtained for T(ij) in principle contain a contribution from J(ij)(aniso), the component along the static applied magnetic field of the anisotropic part of the electron-mediated spin-spin coupling. Neglecting this contribution allows partially averaged dipolar couplings, D(ij), to be extracted from the T(ij), and these were used to determine the structure, orientational order, and the conformational distribution generated by rotation about the C-C bond. The values obtained are compared with the results of calculations by ab initio and density functional methods. The differences found are no greater than those obtained for similar compounds which do not contain fluorine, so that there is no definitive evidence for significant contributions from J(CF)(aniso) or J(FF)(aniso) in the two compounds studied.

An investigation of the structure and bond rotational potential of some fluorinated ethanes by NMR spectroscopy of solutions in nematic liquid crystalline solvents

NASA Astrophysics Data System (ADS)

Emsley, J. W.; Longeri, M.; Merlet, D.; Pileio, G.; Suryaprakash, N.

2006-06-01

NMR spectra of 1,2-dibromo-1,1-difluoroethane and 1-bromo-2-iodo-tetrafluoroethane dissolved in nematic liquid crystalline solvents have been analysed to yield the magnitudes and signs of the scalar couplings, Jij, and total anisotropic couplings, Tij, between all the 1H, 19F, and 13C nuclei, except for those between two 13C nuclei. The values obtained for Tij in principle contain a contribution from Jijaniso, the component along the static applied magnetic field of the anisotropic part of the electron-mediated spin-spin coupling. Neglecting this contribution allows partially averaged dipolar couplings, Dij, to be extracted from the Tij, and these were used to determine the structure, orientational order, and the conformational distribution generated by rotation about the C-C bond. The values obtained are compared with the results of calculations by ab initio and density functional methods. The differences found are no greater than those obtained for similar compounds which do not contain fluorine, so that there is no definitive evidence for significant contributions from JCFaniso or JFFaniso in the two compounds studied.

Intense Current Structures Observed at Electron Kinetic Scales in the Near-Earth Magnetotail During Dipolarization and Substorm Current Wedge Formation

NASA Astrophysics Data System (ADS)

Grigorenko, E. E.; Dubyagin, S.; Malykhin, A. Yu.; Khotyaintsev, Yu V.; Kronberg, E. A.; Lavraud, B.; Ganushkina, N. Yu

2018-01-01

We use data from the 2013-2014 Cluster Inner Magnetosphere Campaign, with its uniquely small spacecraft separations (less than or equal to electron inertia length, λe), to study multiscale magnetic structures in 14 substorm-related prolonged dipolarizations in the near-Earth magnetotail. Three time scales of dipolarization are identified: (i) a prolonged growth of the BZ component with duration ≤20 min; (ii) BZ pulses with durations ≤1 min during the BZ growth; and (iii) strong magnetic field gradients with durations ≤2 s during the dipolarization growth. The values of these gradients observed at electron scales are several dozen times larger than the corresponding values of magnetic gradients simultaneously detected at ion scales. These nonlinear features in magnetic field gradients denote the formation of intense and localized (approximately a few λe) current structures during the dipolarization and substorm current wedge formation. These observations highlight the importance of electron scale processes in the formation of a 3-D substorm current system.

Magnetic braking of stellar cores in red giants and supergiants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maeder, André; Meynet, Georges, E-mail: andre.maeder@unige, E-mail: georges.meynet@unige.ch

2014-10-01

Magnetic configurations, stable on the long term, appear to exist in various evolutionary phases, from main-sequence stars to white dwarfs and neutron stars. The large-scale ordered nature of these fields, often approximately dipolar, and their scaling according to the flux conservation scenario favor a fossil field model. We make some first estimates of the magnetic coupling between the stellar cores and the outer layers in red giants and supergiants. Analytical expressions of the truncation radius of the field coupling are established for a convective envelope and for a rotating radiative zone with horizontal turbulence. The timescales of the internal exchangesmore » of angular momentum are considered. Numerical estimates are made on the basis of recent model grids. The direct magnetic coupling of the core to the extended convective envelope of red giants and supergiants appears unlikely. However, we find that the intermediate radiative zone is fully coupled to the core during the He-burning and later phases. This coupling is able to produce a strong spin down of the core of red giants and supergiants, also leading to relatively slowly rotating stellar remnants such as white dwarfs and pulsars. Some angular momentum is also transferred to the outer convective envelope of red giants and supergiants during the He-burning phase and later.« less

Unique dielectric dipole and hopping ion dipole relaxation in disordered systems

NASA Astrophysics Data System (ADS)

Govindaraj, G.

2018-04-01

Dielectric or ac conductivity measurements of dielectric and ion conducting glass and crystalline systems provide considerable insight into the nature of the dipolar and ionic motions in disordered solids. However, interpreting the dielectric or ac conductivity has been a matter of considerable debate based on the existing models and empirical formalism, particularly in regards to how best to represent the relaxation process that is the result of a transition from correlated to uncorrelated dipolar and ionic motions. A unique dipole interaction process has been proposed for the (a) dielectric dipole process (b) the hopping ion conducting dipole process and the (c) combination (a) and (b) for the description of dielectric spectra and ac conductivityspectra and results are reported.

Berry Curvature in Magnon-Phonon Hybrid Systems.

PubMed

Takahashi, Ryuji; Nagaosa, Naoto

2016-11-18

We study theoretically the Berry curvature of the magnon induced by the hybridization with the acoustic phonons via the spin-orbit and dipolar interactions. We first discuss the magnon-phonon hybridization via the dipolar interaction, and show that the dispersions have gapless points in momentum space, some of which form a loop. Next, when both spin-orbit and dipolar interactions are considered, we show anisotropic texture of the Berry curvature and its divergence with and without gap closing. Realistic evaluation of the consequent anomalous velocity is given for yttrium iron garnet.

Nonlocal and nonlinear electrostatics of a dipolar Coulomb fluid.

PubMed

Sahin, Buyukdagli; Ralf, Blossey

2014-07-16

We study a model Coulomb fluid consisting of dipolar solvent molecules of finite extent which generalizes the point-like dipolar Poisson-Boltzmann model (DPB) previously introduced by Coalson and Duncan (1996 J. Phys. Chem. 100 2612) and Abrashkin et al (2007 Phys. Rev. Lett. 99 077801). We formulate a nonlocal Poisson-Boltzmann equation (NLPB) and study both linear and nonlinear dielectric response in this model for the case of a single plane geometry. Our results shed light on the relevance of nonlocal versus nonlinear effects in continuum models of material electrostatics.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Băloi, Mihaela-Andreea, E-mail: mihaela.baloi88@e-uvt.ro; Crucean, Cosmin

The production of fermions in dipolar electric fields on de Sitter universe is studied. The amplitude and probability of pair production are computed using the exact solution of the Dirac equation in de Sitter spacetime. The form of the dipolar fields is established using the conformal invariance of the Maxwell equations. We obtain that the momentum conservation law is broken in the process of pair production in dipolar electric fields. Also we establish that there are nonvanishing probabilities for processes in which the helicity is conserved/nonconserved. The Minkowski limit is recovered when the expansion factor becomes zero.

1,3-Dipolar Cycloadditions of Diazo Compounds in the Presence of Azides.

PubMed

Aronoff, Matthew R; Gold, Brian; Raines, Ronald T

2016-04-01

The diazo group has untapped utility in chemical biology. The tolerance of stabilized diazo groups to cellular metabolism is comparable to that of azido groups. However, chemoselectivity has been elusive, as both groups undergo 1,3-dipolar cycloadditions with strained alkynes. Removing strain and tuning dipolarophile electronics yields diazo group selective 1,3-dipolar cycloadditions that can be performed in the presence of an azido group. For example, diazoacetamide but not its azido congener react with dehydroalanine residues, as in the natural product nisin.

Synthesis of Trifluoromethylated Isoxazolidines: 1,3-Dipolar Cycloaddition of Nitrosoarenes, (Trifluoromethyl)diazomethane, and Alkenes

PubMed Central

Molander, Gary A.; Cavalcanti, Livia N.

2013-01-01

Isoxazolidines have proven to be important substrates in synthetic organic chemistry. Limited examples in the literature that provide trifluoromethylated versions of these compounds have prompted us to investigate a 1,3-dipolar cycloaddition route providing access to N-functionalized isoxazolidines containing a trifluoromethyl group. Thus, a 1,3-dipolar cycloaddition of nitrosoarenes, (trifluoromethyl)diazomethane, and alkenes was developed. The starting materials can be synthesized from easy to handle and accessible reagents. The reaction proved to be tolerant of a variety of electron-deficient alkenes and nitrosoarenes. PMID:24490778

The structure of ions and zwitterionic lipids regulates the charge of dipolar membranes.

PubMed

Szekely, Or; Steiner, Ariel; Szekely, Pablo; Amit, Einav; Asor, Roi; Tamburu, Carmen; Raviv, Uri

2011-06-21

In pure water, zwitterionic lipids form lamellar phases with an equilibrium water gap on the order of 2 to 3 nm as a result of the dominating van der Waals attraction between dipolar bilayers. Monovalent ions can swell those neutral lamellae by a small amount. Divalent ions can adsorb onto dipolar membranes and charge them. Using solution X-ray scattering, we studied how the structure of ions and zwitterionic lipids regulates the charge of dipolar membranes. We found that unlike monovalent ions that weakly interact with all of the examined dipolar membranes, divalent and trivalent ions adsorb onto membranes containing lipids with saturated tails, with an association constant on the order of ∼10 M(-1). One double bond in the lipid tail is sufficient to prevent divalent ion adsorption. We suggest that this behavior is due to the relatively loose packing of lipids with unsaturated tails that increases the area per lipid headgroup, enabling their free rotation. Divalent ion adsorption links two lipids and limits their free rotation. The ion-dipole interaction gained by the adsorption of the ions onto unsaturated membranes is insufficient to compensate for the loss of headgroup free-rotational entropy. The ion-dipole interaction is stronger for cations with a higher valence. Nevertheless, polyamines behave as monovalent ions near dipolar interfaces in the sense that they interact weakly with the membrane surface, whereas in the bulk their behavior is similar to that of multivalent cations. Advanced data analysis and comparison with theory provide insight into the structure and interactions between ion-induced regulated charged interfaces. This study models biologically relevant interactions between cell membranes and various ions and the manner in which the lipid structure governs those interactions. The ability to monitor these interactions creates a tool for probing systems that are more complex and forms the basis for controlling the interactions between dipolar membranes and charged proteins or biopolymers for encapsulation and delivery applications. © 2011 American Chemical Society

Quantum Theory of Atoms in Molecules Charge-Charge Transfer-Dipolar Polarization Classification of Infrared Intensities.

PubMed

Duarte, Leonardo J; Richter, Wagner E; Silva, Arnaldo F; Bruns, Roy E

2017-10-26

Fundamental infrared vibrational transition intensities of gas-phase molecules are sensitive probes of changes in electronic structure accompanying small molecular distortions. Models containing charge, charge transfer, and dipolar polarization effects are necessary for a successful classification of the C-H, C-F, and C-Cl stretching and bending intensities. C-H stretching and in-plane bending vibrations involving sp 3 carbon atoms have small equilibrium charge contributions and are accurately modeled by the charge transfer-counterpolarization contribution and its interaction with equilibrium charge movement. Large C-F and C═O stretching intensities have dominant equilibrium charge movement contributions compared to their charge transfer-dipolar polarization ones and are accurately estimated by equilibrium charge and the interaction contribution. The C-F and C-Cl bending modes have charge and charge transfer-dipolar polarization contribution sums that are of similar size but opposite sign to their interaction values resulting in small intensities. Experimental in-plane C-H bends have small average intensities of 12.6 ± 10.4 km mol -1 owing to negligible charge contributions and charge transfer-counterpolarization cancellations, whereas their average out-of-plane experimental intensities are much larger, 65.7 ± 20.0 km mol -1 , as charge transfer is zero and only dipolar polarization takes place. The C-F bending intensities have large charge contributions but very small intensities. Their average experimental out-of-plane intensity of 9.9 ± 12.6 km mol -1 arises from the cancellation of large charge contributions by dipolar polarization contributions. The experimental average in-plane C-F bending intensity, 5.8 ± 7.3 km mol -1 , is also small owing to charge and charge transfer-counterpolarization sums being canceled by their interaction contributions. Models containing only atomic charges and their fluxes are incapable of describing electronic structure changes for simple molecular distortions that are of interest in classifying infrared intensities. One can expect dipolar polarization effects to also be important for larger distortions of chemical interest.

Direct 1H NMR evidence of spin-rotation coupling as a source of para → ortho-H2 conversion in diamagnetic solvents

NASA Astrophysics Data System (ADS)

Terenzi, Camilla; Bouguet-Bonnet, Sabine; Canet, Daniel

2017-04-01

At ambient temperature, conversion from 100% enriched para-hydrogen (p-H2; singlet state) to ortho-hydrogen (o-H2; triplet state) leads necessarily to the thermodynamic equilibrium proportions: 75% of o-H2 and 25% of p-H2. When p-H2 is dissolved in a diamagnetic organic solvent, conversion is very slow and can be considered as arising from nuclear spin relaxation phenomena. A first relaxation mechanism, specific to the singlet state and involving a combination of auto-correlation and cross correlation spectral densities, can be retained: randomly fluctuating magnetic fields due to inter-molecular dipolar interactions. We demonstrate here that (i) this dipolar mechanism is not sufficient for accounting for the p a r a →o r t h o conversion rate, (ii) spin-rotation interaction, an intra-molecular mechanism, behaves similarly to random-field interaction and, thus, may be involved in the singlet relaxation rate. Also, as the p a r a →o r t h o conversion is monitored by proton nuclear magnetic resonance (NMR) of dissolved o-H2 (p-H2 is NMR-silent), one has to account for H2 exchange between the liquid phase and the gas phase within the NMR tube, as well as for dissolution effects. Experimental evidence of the above statements is brought here in the case of two organic solvents: acetone-d6 and carbon disulfide. The observed temperature dependence of the p a r a →o r t h o conversion rate shows that spin-rotation can be the dominant contribution to the p-H2 relaxation rate in the absence of tangible dipolar interactions. Our findings shed new light on the "mysterious" mechanism of the p a r a →o r t h o conversion which has been searched for several decades.

Dipolar eddies in a decaying stratified turbulent flow

NASA Astrophysics Data System (ADS)

Voropayev, S. I.; Fernando, H. J. S.; Morrison, R.

2008-02-01

Laboratory experiments on the evolution of dipolar (momentum) eddies in a stratified fluid in the presence of random background motions are described. A turbulent jet puff was used to generate the momentum eddies, and a decaying field of ambient random vortical motions was generated by a towed grid. Data on vorticity/velocity fields of momentum eddies, those of background motions, and their interactions were collected in the presence and absence of the other, and the main characteristics thereof were parametrized. Similarity arguments predict that dipolar eddies in stratified fluids may preserve their identity in decaying grid-generated stratified turbulence, which was verified experimentally. Possible applications of the results include mushroomlike currents and other naturally/artificially generated large dipolar eddies in strongly stratified layers of the ocean, the longevity of which is expected to be determined by the characteristics of the eddies and random background motions.

Quantum phases of dipolar soft-core bosons

NASA Astrophysics Data System (ADS)

Grimmer, D.; Safavi-Naini, A.; Capogrosso-Sansone, B.; Söyler, Ş. G.

2014-10-01

We study the phase diagram of a system of soft-core dipolar bosons confined to a two-dimensional optical lattice layer. We assume that dipoles are aligned perpendicular to the layer such that the dipolar interactions are purely repulsive and isotropic. We consider the full dipolar interaction and perform path-integral quantum Monte Carlo simulations using the worm algorithm. Besides a superfluid phase, we find various solid and supersolid phases. We show that, unlike what was found previously for the case of nearest-neighbor interaction, supersolid phases are stabilized by doping the solids not only with particles but with holes as well. We further study the stability of these quantum phases against thermal fluctuations. Finally, we discuss pair formation and the stability of the pair checkerboard phase formed in a bilayer geometry, and we suggest experimental conditions under which the pair checkerboard phase can be observed.

Improved heteronuclear dipolar decoupling sequences for liquid-crystal NMR

NASA Astrophysics Data System (ADS)

Thakur, Rajendra Singh; Kurur, Narayanan D.; Madhu, P. K.

2007-04-01

Recently we introduced a radiofrequency pulse scheme for heteronuclear dipolar decoupling in solid-state nuclear magnetic resonance under magic-angle spinning [R.S. Thakur, N.D. Kurur, P.K. Madhu, Swept-frequency two-pulse phase modulation for heteronuclear dipolar decoupling in solid-state NMR, Chem. Phys. Lett. 426 (2006) 459-463]. Variants of this sequence, swept-frequency TPPM, employing frequency modulation of different types have been further tested to improve the efficiency of heteronuclear dipolar decoupling. Among these, certain sequences that were found to perform well at lower spinning speeds are demonstrated here on a liquid-crystal sample of MBBA for application in static samples. The new sequences are compared with the standard TPPM and SPINAL schemes and are shown to perform better than them. These modulated schemes perform well at low decoupler radiofrequency power levels and are easy to implement on standard spectrometers.

Linear polarimetry of AP stars. IV. The influence of deviations from a pure dipolar model.

NASA Astrophysics Data System (ADS)

Leroy, J. L.; Landolfi, M.; Landi Degl'Innocenti, M.; Landi Degl'Innocenti, E.; Bagnulo, S.; Laporte, P.

1995-09-01

In the previous papers of this series we have described a new observational program of broadband linear polarimetry aimed at Ap stars. At the same time, we have established a canonical model, based on the oblique rotator geometry, which describes successfully the main features of the observed polarization: in some cases the linear polarization data, combined with the classical circular polarization measurements, allow one to determine the characteristic parameters which define the oblique dipolar rotator. However, we have also observed polarization diagrams that depart clearly from those predicted by the canonical model, which means that it is not always possible to rely on a pure dipolar model (nor on a combination of a dipole plus a linear quadrupole parallel to the dipole). Although an interpretation of the polarization peculiarities in terms of magnetic `anomalies' (i.e. deviations from the dipolar configuration) is quite natural, one must also take into account the possible influence of local abundance inhomogeneities. Therefore, we have first studied the sensitivity of the polarized signal (which is known to be due to the differential saturation of Zeeman components in spectral lines) to a variation of the metallic absorption spectrum. Then we have examined how a local enhancement (or reduction) of the polarization produced by a dipolar magnetic field affects the Fourier spectrum of the observed polarization signal. Finally, we have designed an inversion program making possible the recovery - under certain restrictions - of the spatial modulations of the polarization generated by a dipole, which are necessary to explain `odd' polarimetric data. This program has been applied to the data gathered from three stars (49 Cam, β CrB, HD 71866). As far as the last star is concerned, none of the spatial modulations considered was able to reproduce the observations. On the contrary, good solutions are found for the other two. However, if one interprets the variations of the polarization as the result of abundance variations, which must correspond to a modulation of the absorption spectrum, a contradiction arises, especially for β CrB, because the observed spectral variability of these stars is too small to account for our computed maps. Therefore, non-canonical polarization diagrams must essentially be interpreted in terms of magnetic anomalies, not of abundance anomalies: in other words, the peculiarities of the polarization diagrams are likely to result mainly from departures of the magnetic configuration from the pure dipolar configuration.

Chain Dynamics in Magnetorheological Suspensions

NASA Technical Reports Server (NTRS)

Gast, A. P.; Furst, E. M.

1999-01-01

Magnetorheological (MR) suspensions are composed of colloidal particles which acquire dipole moments when subjected to an external magnetic field. At sufficient field strengths and concentrations, the dipolar particles rapidly aggregate to form long chains. Subsequent lateral cross-linking of the dipolar chains is responsible for a rapid liquid-to-solid-like rheological transition. The unique, magnetically-activated rheological properties of MR suspensions make them ideal for interfacing mechanical systems to electronic controls. Additionally, the ability to experimentally probe colloidal suspensions interacting through tunable anisotropic potentials is of fundamental interest. Our current experimental work has focused on understanding the fluctuations of dipolar chains. It has been proposed by Halsey and Toor (HT) that the strong Landau-Peierls thermal fluctuations of dipolar chains could be responsible for long-range attractions between chains. Such interactions will govern the long-time relaxation of MR suspensions. We have synthesized monodisperse neutrally buoyant MR suspensions by density matching stabilized ferrofluid emulsion droplets with D2O. This allows us to probe the dynamics of the dipolar chains using light scattering without gravitational, interfacial, and polydispersity effects to resolve the short-wavelength dynamics of the dipolar chains. We used diffusing wave spectroscopy to measure these dynamics. The particle displacements at short times that show an independence to the field strength, but at long times exhibit a constrained, sub-diffusive motion that slows as the dipole strength is increased. The experiments are in good qualitative agreement with Brownian dynamics simulations of dipolar chains. Although there have been several important and detailed studies of the structure and interactions in MR suspensions, there has not been conclusive evidence that supports or contradicts the HT model prediction that long-range interactions exist between fluctuating chains of dipolar particles. Resolving this issue would contribute greatly to the understanding of these interesting and important materials. We have begun to test the predictions of the HT model by both examining the dynamics of individual chains and by measuring the forces between dipolar chains directly to accurately and quantitatively assess the interactions that they experience. To do so, we employ optical trapping techniques and video-microscopy to manipulate and observe our samples on the microscopic level. With these techniques, it is possible to observe chains that are fluctuating freely in three-dimensions, independent of interfacial effects. More importantly, we are able to controllably observe the interactions of two chains at various separations to measure the force-distance profile. The techniques also allow us to study the mechanical properties of individual chains and chain clusters. Our work to this point has focused on reversibly-formed dipolar chains due to field induced dipoles where the combination of this chaining, the dipolar forces, and the hydrodynamic interactions that dictate the rheology of the suspensions. One can envision, however, many situations where optical, electronic, or rheological behavior may be optimized with magneto-responsive anisotropic particles. Chains of polarizable particles may have the best properties as they can coil and flex in the absence of a field and stiffen and orient when a field is applied. We have recently demonstrated a synthesis of stable, permanent paramagnetic chains by both covalently and physically linking paramagnetic colloidal particles. The method employed allows us to create monodisperse chains of controlled length. We observed the stability, field-alignment, and rigidity of this new class of materials. The chains may exhibit unique rheological properties in an applied magnetic field over isotropic suspensions of paramagnetic particles. They are also useful rheological models as bead-spring systems. These chains form the basis for our current experiments with optical traps.

Entanglement and co-tunneling of two equivalent protons in hydrogen bond pairs

NASA Astrophysics Data System (ADS)

Smedarchina, Zorka; Siebrand, Willem; Fernández-Ramos, Antonio

2018-03-01

A theoretical study is reported of a system of two identical symmetric hydrogen bonds, weakly coupled such that the two mobile protons can move either separately (stepwise) or together (concerted). It is modeled by two equivalent quartic potentials interacting through dipolar and quadrupolar coupling terms. The tunneling Hamiltonian has two imaginary modes (reaction coordinates) and a potential with a single maximum that may turn into a saddle-point of second order and two sets of (inequivalent) minima. Diagonalization is achieved via a modified Jacobi-Davidson algorithm. From this Hamiltonian the mechanism of proton transfer is derived. To find out whether the two protons move stepwise or concerted, a new tool is introduced, based on the distribution of the probability flux in the dividing plane of the transfer mode. While stepwise transfer dominates for very weak coupling, it is found that concerted transfer (co-tunneling) always occurs, even when the coupling vanishes since the symmetry of the Hamiltonian imposes permanent entanglement on the motions of the two protons. We quantify this entanglement and show that, for a wide range of parameters of interest, the lowest pair of states of the Hamiltonian represents a perfect example of highly entangled quantum states in continuous variables. The method is applied to the molecule porphycene for which the observed tunneling splitting is calculated in satisfactory agreement with experiment, and the mechanism of double-proton tunneling is found to be predominantly concerted. We show that, under normal conditions, when they are in the ground state, the two porphycene protons are highly entangled, which may have interesting applications. The treatment also identifies the conditions under which such a system can be handled by conventional one-instanton techniques.

Dynamic nuclear polarization assisted spin diffusion for the solid effect case.

PubMed

Hovav, Yonatan; Feintuch, Akiva; Vega, Shimon

2011-02-21

The dynamic nuclear polarization (DNP) process in solids depends on the magnitudes of hyperfine interactions between unpaired electrons and their neighboring (core) nuclei, and on the dipole-dipole interactions between all nuclei in the sample. The polarization enhancement of the bulk nuclei has been typically described in terms of a hyperfine-assisted polarization of a core nucleus by microwave irradiation followed by a dipolar-assisted spin diffusion process in the core-bulk nuclear system. This work presents a theoretical approach for the study of this combined process using a density matrix formalism. In particular, solid effect DNP on a single electron coupled to a nuclear spin system is considered, taking into account the interactions between the spins as well as the main relaxation mechanisms introduced via the electron, nuclear, and cross-relaxation rates. The basic principles of the DNP-assisted spin diffusion mechanism, polarizing the bulk nuclei, are presented, and it is shown that the polarization of the core nuclei and the spin diffusion process should not be treated separately. To emphasize this observation the coherent mechanism driving the pure spin diffusion process is also discussed. In order to demonstrate the effects of the interactions and relaxation mechanisms on the enhancement of the nuclear polarization, model systems of up to ten spins are considered and polarization buildup curves are simulated. A linear chain of spins consisting of a single electron coupled to a core nucleus, which in turn is dipolar coupled to a chain of bulk nuclei, is considered. The interaction and relaxation parameters of this model system were chosen in a way to enable a critical analysis of the polarization enhancement of all nuclei, and are not far from the values of (13)C nuclei in frozen (glassy) organic solutions containing radicals, typically used in DNP at high fields. Results from the simulations are shown, demonstrating the complex dependences of the DNP-assisted spin diffusion process on variations of the relevant parameters. In particular, the effect of the spin lattice relaxation times on the polarization buildup times and the resulting end polarization are discussed, and the quenching of the polarizations by the hyperfine interaction is demonstrated.

An explanation of auroral intensification during the substorm expansion phase

NASA Astrophysics Data System (ADS)

Yao, Zhonghua; Rae, I. J.; Lui, A. T. Y.; Murphy, K. R.; Owen, C. J.; Pu, Z. Y.; Forsyth, C.; Grodent, D.; Zong, Q.-G.; Du, A. M.; Kalmoni, N. M. E.

2017-08-01

A multiple auroral onset substorm on 28 March 2010 provides an opportunity to understand the physical mechanism in generating auroral intensifications during a substorm expansion phase. Conjugate observations of magnetic fields and plasma from the Time History of Events and Macroscale Interactions during Substorms (THEMIS) spacecraft, of field-aligned currents (FACs) from the Active Magnetosphere and Planetary Electrodynamics Response Experiment (AMPERE) satellites, and from ground-based magnetometers and aurora are all available. The comprehensive measurements allow us to further our understanding of the complicated causalities among dipolarization, FAC generation, particle acceleration, and auroral intensification. During the substorm expansion phase, the plasma sheet expanded and was perturbed leading to the generation of a slow mode wave, which modulated electron flux in the outer plasma sheet. During this current sheet expansion, field-aligned currents formed, and geomagnetic perturbations were simultaneously detected by ground-based instruments. However, a magnetic dipolarization did not occur until about 3 min later in the outer plasma sheet observed by THEMIS-A spacecraft (THA). We believe that this dipolarization led to an efficient Fermi acceleration to electrons and consequently the cause of a significant auroral intensification during the expansion phase as observed by the All-Sky Imagers (ASIs). This Fermi acceleration mechanism operating efficiently in the outer plasma sheet during the expansion phase could be a common explanation of the poleward auroral development after substorm onset. These results also show a good agreement between the upward FAC derived from AMPERE measurements and the auroral brightening observed by the ASIs.

Dipolar ferromagnetic phase transition in Fe3O4 nanoparticle arrays observed by Lorentz microscopy and electron holography

NASA Astrophysics Data System (ADS)

Yamamoto, Kazuo; Hogg, Charles R.; Yamamuro, Saeki; Hirayama, Tsukasa; Majetich, Sara A.

2011-02-01

Dipolar ferromagnetism formed in Fe3O4 nanoparticle arrays is revealed by Fresnel Lorentz microscopy and electron holography. Dipolar domain walls do not lie preferentially along macrograin boundaries but depend on the overall shape of the assembly, meaning magnetostatic energy dominates. The domain structures are imaged at different temperatures for both monolayer and bilayer arrays. The domain wall contrast in the monolayer region is visible until 575 °C, and the magnetic order parameter steeply drops toward the temperature. In the bilayer region, finer and more complicated domains are formed.

Dipolar particles in a double-trap confinement: Response to tilting the dipolar orientation

NASA Astrophysics Data System (ADS)

Bjerlin, J.; Bengtsson, J.; Deuretzbacher, F.; Kristinsdóttir, L. H.; Reimann, S. M.

2018-02-01

We analyze the microscopic few-body properties of dipolar particles confined in two parallel quasi-one-dimensional harmonic traps. In particular, we show that an adiabatic rotation of the dipole orientation about the trap axes can drive an initially nonlocalized few-fermion state into a localized state with strong intertrap pairing. With an instant, nonadiabatic rotation, however, localization is inhibited and a highly excited state is reached. This state may be interpreted as the few-body analog of a super-Tonks-Girardeau state, known from one-dimensional systems with contact interactions.

Gas-liquid coexistence in a system of dipolar soft spheres.

PubMed

Jia, Ran; Braun, Heiko; Hentschke, Reinhard

2010-12-01

The existence of gas-liquid coexistence in dipolar fluids with no other contribution to attractive interaction than dipole-dipole interaction is a basic and open question in the theory of fluids. Here we compute the gas-liquid critical point in a system of dipolar soft spheres subject to an external electric field using molecular dynamics computer simulation. Tracking the critical point as the field strength is approaching zero we find the following limiting values: T(c)=0.063 and ρ(c)=0.0033 (dipole moment μ=1). These values are confirmed by independent simulation at zero field strength.

Ground-state candidate for the classical dipolar kagome Ising antiferromagnet

NASA Astrophysics Data System (ADS)

Chioar, I. A.; Rougemaille, N.; Canals, B.

2016-06-01

We have investigated the low-temperature thermodynamic properties of the classical dipolar kagome Ising antiferromagnet using Monte Carlo simulations, in the quest for the ground-state manifold. In spite of the limitations of a single-spin-flip approach, we managed to identify certain ordering patterns in the low-temperature regime and we propose a candidate for this unknown state. This configuration presents some intriguing features and is fully compatible with the extrapolations of the at-equilibrium thermodynamic behavior sampled so far, making it a very likely choice for the dipolar long-range ordered state of the classical kagome Ising antiferromagnet.

Spin coherence in a Mn3 single-molecule magnet

NASA Astrophysics Data System (ADS)

Abeywardana, Chathuranga; Mowson, Andrew M.; Christou, George; Takahashi, Susumu

2016-01-01

Spin coherence in single crystals of the spin S = 6 single-molecule magnet (SMM) [Mn3O(O2CEt)3(mpko)3]+ (abbreviated Mn3) has been investigated using 230 GHz electron paramagnetic resonance spectroscopy. Coherence in Mn3 was uncovered by significantly suppressing dipolar contribution to the decoherence with complete spin polarization of Mn3 SMMs. The temperature dependence of spin decoherence time (T2) revealed that the dipolar decoherence is the dominant source of decoherence in Mn3 and T2 can be extended up to 267 ns by quenching the dipolar decoherence.

Designing dipolar recoupling and decoupling experiments for biological solid-state NMR using interleaved continuous wave and RF pulse irradiation.

PubMed

Bjerring, Morten; Jain, Sheetal; Paaske, Berit; Vinther, Joachim M; Nielsen, Niels Chr

2013-09-17

Rapid developments in solid-state NMR methodology have boosted this technique into a highly versatile tool for structural biology. The invention of increasingly advanced rf pulse sequences that take advantage of better hardware and sample preparation have played an important part in these advances. In the development of these new pulse sequences, researchers have taken advantage of analytical tools, such as average Hamiltonian theory or lately numerical methods based on optimal control theory. In this Account, we focus on the interplay between these strategies in the systematic development of simple pulse sequences that combines continuous wave (CW) irradiation with short pulses to obtain improved rf pulse, recoupling, sampling, and decoupling performance. Our initial work on this problem focused on the challenges associated with the increasing use of fully or partly deuterated proteins to obtain high-resolution, liquid-state-like solid-state NMR spectra. Here we exploit the overwhelming presence of (2)H in such samples as a source of polarization and to gain structural information. The (2)H nuclei possess dominant quadrupolar couplings which complicate even the simplest operations, such as rf pulses and polarization transfer to surrounding nuclei. Using optimal control and easy analytical adaptations, we demonstrate that a series of rotor synchronized short pulses may form the basis for essentially ideal rf pulse performance. Using similar approaches, we design (2)H to (13)C polarization transfer experiments that increase the efficiency by one order of magnitude over standard cross polarization experiments. We demonstrate how we can translate advanced optimal control waveforms into simple interleaved CW and rf pulse methods that form a new cross polarization experiment. This experiment significantly improves (1)H-(15)N and (15)N-(13)C transfers, which are key elements in the vast majority of biological solid-state NMR experiments. In addition, we demonstrate how interleaved sampling of spectra exploiting polarization from (1)H and (2)H nuclei can substantially enhance the sensitivity of such experiments. Finally, we present systematic development of (1)H decoupling methods where CW irradiation of moderate amplitude is interleaved with strong rotor-synchronized refocusing pulses. We show that these sequences remove residual cross terms between dipolar coupling and chemical shielding anisotropy more effectively and improve the spectral resolution over that observed in current state-of-the-art methods.

Shape Transitions and Lattice Structuring of Ceramide-Enriched Domains Generated by Sphingomyelinase in Lipid Monolayers

PubMed Central

Härtel, Steffen; Fanani, María Laura; Maggio, Bruno

2005-01-01

Sphingomyelinases (SMases) hydrolyze the membrane constituent sphingomyelin (SM) to phosphocholine and ceramide (Cer). Growing evidence supports that SMase-induced SM→Cer conversion leads to the formation of lateral Cer-enriched domains which drive structural reorganization in lipid membranes. We previously provided visual evidence in real-time for the formation of Cer-enriched domains in SM monolayers through the action of the neutral Bacillus cereus SMase. In this work, we disclose a succession of discrete morphologic transitions and lateral organization of Cer-enriched domains that underlay the SMase-generated surface topography. We further reveal how these structural parameters couple to the generation of two-dimensional electrostatic fields, based upon the specific orientation of the lipid dipole moments in the Cer-enriched domains. Advanced image processing routines in combination with time-resolved epifluorescence microscopy on Langmuir monolayers revealed: 1), spontaneous nucleation and circular growth of Cer-enriched domains after injection of SMase into the subphase of the SM monolayer; 2), domain-intrinsic discrete transitions from circular to periodically undulating shapes followed by a second transition toward increasingly branched morphologies; 3), lateral superstructure organization into predominantly hexagonal domain lattices; 4), formation of super-superstructures by the hexagonal lattices; and 5), rotationally and laterally coupled domain movement before domain border contact. All patterns proved to be specific for the SMase-driven system since they could not be observed with Cer-enriched domains generated by defined mixtures of SM/Cer in enzyme-free monolayers at the same surface pressure (Π = 10 mN/m). Following the theories of lateral shape transitions, dipolar electrostatic interactions of lipid domains, and direct determinations of the monolayer dipole potential, our data show that SMase induces a domain-specific packing and orientation of the molecular dipole moments perpendicular to the air/water interface. In consequence, protein-driven generation of specific out-of-equilibrium states, an accepted concept for maintenance of transmembrane lipid asymmetry, must also be considered on the lateral level. Lateral enzyme-specific out-of-equilibrium organization of lipid domains represents a new level of signal transduction from local (nm) to long-range (μm) scales. The cross-talk between lateral domain structures and dipolar electrostatic fields adds new perspectives to the mechanisms of SMase-mediated signal transduction in biological membranes. PMID:15489298

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gottwald, M.; Kan, J. J.; Lee, K.

Thermal budget, stack thickness, and dipolar offset field control are crucial for seamless integration of perpendicular magnetic junctions (pMTJ) into semiconductor integrated circuits to build scalable spin-transfer-torque magnetoresistive random access memory. This paper is concerned with materials and process tuning to deliver thermally robust (400 °C, 30 min) and thin (i.e., fewer layers and integration-friendly) pMTJ utilizing Co/Pt-based bottom pinned layers. Interlayer roughness control is identified as a key enabler to achieve high thermal budgets. The dipolar offset fields of the developed film stacks at scaled dimensions are evaluated by micromagnetic simulations. This paper shows a path towards achieving sub-15 nm-thick pMTJ withmore » tunneling magnetoresistance ratio higher than 150% after 30 min of thermal excursion at 400 °C.« less

Controlling electric, magnetic, and chiral dipolar emission with PT-symmetric potentials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alaeian, Hadiseh; Dionne, Jennifer A.

We investigate the effect of parity-time (PT) symmetric optical potentials on the radiation of achiral and chiral dipole sources. Two properties unique to PT-symmetric potentials are observed. First, the dipole can be tuned to behave as a strong optical emitter or absorber based on the non-Hermiticity parameter and the dipole location. Second, exceptional points give rise to new system resonances that lead to orders-of-magnitude enhancements in the dipolar emitted or absorbed power. Utilizing these properties, we show that enantiomers of chiral molecules near PT-symmetric metamaterials exhibit a 4.5-fold difference in their emitted power and decay rate. The results of thismore » work could enable new atom-cavity interactions for quantum optics, as well as all-optical enantioselective separation.« less

Design, synthesis, and characterization of photoinitiators for two-photon polymerization

NASA Astrophysics Data System (ADS)

Whitby, Reece; MacMillan, Ryan; Janssens, Stefaan; Raymond, Sebastiampillai; Clarke, Dave; Kay, Andrew; Jin, Jianyong; Simpson, Cather M.

2016-09-01

A series of dipolar and quadrupolar two-photon absorption (2PA) photoinitiators (PIs) based around the well-known triphenylamine (TPA) core and tricyanofuran (TCF) acceptors have been prepared for use in two-photon polymerisation (TPP). The synthesised dipolar species are designated as 5 and 7, and the remaining quadrupolar species are 6, 8, 9 and 10. Large two-photon absorption cross-sections (δ2PA) ranging between 333 - 507 GM were measured at 780 nm using the z-scan technique. Fluorescence quantum yields (ΦF) were below 3% across the series when compared to Rhodamine 6G as a reference standard. Finally, TPP tests were conducted on PIs 7 and 8 to assess their ability to initiate the polymerisation of acrylate monomers using an 800 nm femtosecond Ti:Sapphire laser system.

Van Allen Probes observations of magnetic field dipolarization and its associated O + flux variations in the inner magnetosphere at L<6.6: Dipolarization in Inner Magnetosphere

DOE PAGES

Nosé, M.; Keika, K.; Kletzing, C. A.; ...

2016-07-20

Here we investigate the magnetic field dipolarization in the inner magnetosphere and its associated ion flux variations, using the magnetic field and energetic ion flux data acquired by the Van Allen Probes. From a study of 74 events that appeared at L=4.5–6.6 between 1 October 2012 and 31 October 2013, we reveal the following characteristics of the dipolarization in the inner magnetosphere: (1) its time scale is approximately 5 min; (2) it is accompanied by strong magnetic fluctuations that have a dominant frequency close to the O + gyrofrequency; (3) ion fluxes at 20–50 keV are simultaneously enhanced with largermore » magnitudes for O + than for H +; (4) after a few minutes of the dipolarization, the flux enhancement at 0.1–5keV appears with a clear energy-dispersion signature only for O +; and (5) the energy-dispersed O + flux enhancement appears in directions parallel or antiparallel to the magnetic field. From these characteristics, we discuss possible mechanisms that can provide selective acceleration to O + ions at >20keV. We conclude that O + ions at L = 5.4–6.6 undergo nonadiabatic local acceleration caused by oscillating electric field associated with the magnetic fluctuations and/or adiabatic convective transport from the plasma sheet to the inner magnetosphere by the impulsive electric field. At L = 4.5–5.4, however, only the former acceleration is plausible. Finally, we also conclude that the field-aligned energy-dispersed O + ions at 0.1–5 keV originate from the ionosphere and are extracted nearly simultaneously to the onset of the dipolarization.« less

Van Allen Probes observations of magnetic field dipolarization and its associated O + flux variations in the inner magnetosphere at L<6.6: Dipolarization in Inner Magnetosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nosé, M.; Keika, K.; Kletzing, C. A.

Here we investigate the magnetic field dipolarization in the inner magnetosphere and its associated ion flux variations, using the magnetic field and energetic ion flux data acquired by the Van Allen Probes. From a study of 74 events that appeared at L=4.5–6.6 between 1 October 2012 and 31 October 2013, we reveal the following characteristics of the dipolarization in the inner magnetosphere: (1) its time scale is approximately 5 min; (2) it is accompanied by strong magnetic fluctuations that have a dominant frequency close to the O + gyrofrequency; (3) ion fluxes at 20–50 keV are simultaneously enhanced with largermore » magnitudes for O + than for H +; (4) after a few minutes of the dipolarization, the flux enhancement at 0.1–5keV appears with a clear energy-dispersion signature only for O +; and (5) the energy-dispersed O + flux enhancement appears in directions parallel or antiparallel to the magnetic field. From these characteristics, we discuss possible mechanisms that can provide selective acceleration to O + ions at >20keV. We conclude that O + ions at L = 5.4–6.6 undergo nonadiabatic local acceleration caused by oscillating electric field associated with the magnetic fluctuations and/or adiabatic convective transport from the plasma sheet to the inner magnetosphere by the impulsive electric field. At L = 4.5–5.4, however, only the former acceleration is plausible. Finally, we also conclude that the field-aligned energy-dispersed O + ions at 0.1–5 keV originate from the ionosphere and are extracted nearly simultaneously to the onset of the dipolarization.« less

Stacking of purines in water: the role of dipolar interactions in caffeine.

PubMed

Tavagnacco, L; Di Fonzo, S; D'Amico, F; Masciovecchio, C; Brady, J W; Cesàro, A

2016-05-11

During the last few decades it has been ascertained that base stacking is one of the major contributions stabilizing nucleic acid conformations. However, the understanding of the nature of the interactions involved in the stacking process remains under debate and it is a subject of theoretical and experimental studies. Structural similarity between purine bases (guanine and adenine) in DNA and the caffeine molecule makes caffeine an excellent model for the purine bases. The present study clearly shows that dipolar interactions play a fundamental role in determining stacking of purine molecules in solution. In order to reach this achievement, polarized ultraviolet Raman resonant scattering experiments have been carried out on caffeine aqueous solutions as a function of concentration and temperature. The investigation pointed out at the aggregation and solvation properties, particularly at elevated temperatures. Kubo-Anderson theory was used as a framework to investigate the non-coincidence effect (NCE) occurring in the totally symmetric breathing modes of the purine rings, and in the bending modes of the methyl groups of caffeine. The NCE concentration dependence shows that caffeine aggregation at 80 °C occurs by planar stacking of the hydrophobic faces. The data clearly indicate that dipolar interactions determine the reorientational motion of the molecules in solution and are the driving force for the stacking of caffeine. In parallel, the observed dephasing times imply a change in caffeine interactions as a function of temperature and concentration. A decrease, at low water content, of the dephasing time for the ring breathing vibration mode indicates that self-association alters the solvation structure that is detectable at low concentration. These results are in agreement with simulation predictions and serve as an important validation of the models used in those calculations.

A saponification-triggered gelation of ester-based Zn(II) complex through conformational transformations.

PubMed

Kumar, Ashish; Dubey, Mrigendra; Kumar, Amit; Pandey, Daya Shankar

2014-09-11

Novel saponification-triggered gelation in an ester-based bis-salen Zn(II) complex (1) is described. Strategic structural modifications induced by NaOH in 1 tune the dipolar-/π-interactions leading to J-aggregation and the creation of an inorganic gel material (IGM), which has been established by photophysical, DFT and rheological studies.

Ultrafast responses of dipolar and V-shaped dipicolinate derivatives with potential applications in the labeling of biomolecules

NASA Astrophysics Data System (ADS)

Wang, Yaochuan; Liu, Siyuan; Liu, Dajun; Wang, Guiqiu; Xiao, Haibo

2016-02-01

A dipolar dipicolinate derivative, trans-dimethyl-4-[4'-(N,N-diphenylamino)-styry1]-pyridin-2,6-dicarboxylate (P-1), and a P-1based V-shaped compound, {4-[(E)-2-(2,6-dimethoxycarbonylpyridin-4-yl) vinyl]}-N-phenyl-N-{4-[(E)-2-(2,6-dimethoxycarbonylpyridin-4-yl)vinylphenyl]}aniline (P-2), with intense two-photon fluorescence emission properties were systematically investigated by using steady-state absorption and fluorescence spectroscopy, open-aperture Z-scans, and two-photon excited fluorescence (TPF). The two-photon absorption cross-section of the V-shaped compound P-2 in tetrahydrofuran (THF) was determined to be 208 GM, which represents a 6.5-fold enhancement compared with its dipolar counterpart P-1 (32 GM). Extension of the intramolecular charge transfer (ICT) in the V-shaped dipicolinate derivative has been suggested as the mechanism of enhancement. The excited state dynamics from transient absorption spectroscopy were analyzed and discussed. The formation and relaxation lifetimes of the ICT state for these dipicolinate derivatives in THF solutions were found to be several picoseconds and several hundred picoseconds, respectively. The results show an increased ICT character of the V-shaped compound and a potential application for this compound in two-photon fluorescence imaging fields.

Two-dimensional dispersion of magnetostatic volume spin waves

NASA Astrophysics Data System (ADS)

Buijnsters, Frank J.; van Tilburg, Lennert J. A.; Fasolino, Annalisa; Katsnelson, Mikhail I.

2018-06-01

Owing to the dipolar (magnetostatic) interaction, long-wavelength spin waves in in-plane magnetized films show an unusual dispersion behavior, which can be mathematically described by the model of and and refinements thereof. However, solving the two-dimensional dispersion requires the evaluation of a set of coupled transcendental equations and one has to rely on numerics. In this work, we present a systematic perturbative analysis of the spin wave model. An expansion in the in-plane wavevector allows us to obtain explicit closed-form expressions for the dispersion relation and mode profiles in various asymptotic regimes. Moreover, we derive a very accurate semi-analytical expression for the dispersion relation of the lowest-frequency mode that is straightforward to evaluate.

Dipolarization in the inner magnetosphere during a geomagnetic storm on 7 October 2015

NASA Astrophysics Data System (ADS)

Matsui, H.; Erickson, P. J.; Foster, J. C.; Torbert, R. B.; Argall, M. R.; Anderson, B. J.; Blake, J. B.; Cohen, I. J.; Ergun, R.; Farrugia, C. J.; Khotyaintsev, Y. V.; Korth, H.; Lindqvist, P. A.; Magnes, W.; Marklund, G. T.; Mauk, B.; Paulson, K. W.; Russell, C.; Strangeway, R. J.; Turner, D. L.

2016-12-01

A dipolarization event was observed by the Magnetospheric Multiscale (MMS) spacecraft at L=3.8 and 19.8 magnetic local time (MLT) starting at 23:42:36 UT on 7 October 2015. The magnetic and electric fields showed initially coherent variations between the spacecraft. The sunward convection turned tailward after the dipolarization. The observation is interpreted in terms of the pressure balance or the momentum equation. This was followed by a region traversed where the fields were irregular. The scale length was of the order of the ion gyroradius, suggesting the kinetic nature of the fluctuations. Combination of the multi-instrument, multi-spacecraft data reveals a more detailed picture of the dipolarization event in the inner magnetosphere. Conjunction ionosphere-plasmasphere observations from DMSP, two-dimensional GPS TEC, the Millstone Hill mid-latitude incoherent scatter radar, and AMPERE measurements imply that MMS observations are located on the poleward edge of the ionospheric trough where Region 2 field aligned currents flow.

Dipolarization in the inner magnetosphere during a geomagnetic storm on 7 October 2015

NASA Astrophysics Data System (ADS)

Matsui, H.; Erickson, P. J.; Foster, J. C.; Torbert, R. B.; Argall, M. R.; Anderson, B. J.; Blake, J. B.; Cohen, I. J.; Ergun, R. E.; Farrugia, C. J.; Khotyaintsev, Yu. V.; Korth, H.; Lindqvist, P.-A.; Magnes, W.; Marklund, G. T.; Mauk, B. H.; Paulson, K. W.; Russell, C. T.; Strangeway, R. J.; Turner, D. L.

2016-09-01

A dipolarization event was observed by the Magnetospheric Multiscale (MMS) spacecraft at L = 3.8 and 19.8 magnetic local time starting at ˜23:42:36 UT on 7 October 2015. The magnetic and electric fields showed initially coherent variations between the spacecraft. The sunward convection turned tailward after the dipolarization. The observation is interpreted in terms of the pressure balance or the momentum equation. This was followed by a region traversed where the fields were irregular. The scale length was of the order of the ion gyroradius, suggesting the kinetic nature of the fluctuations. Combination of the multi-instrument, multispacecraft data reveals a more detailed picture of the dipolarization event in the inner magnetosphere. Conjunction ionosphere-plasmasphere observations from DMSP, two-dimensional GPS total electron content, the Millstone Hill midlatitude incoherent scatter radar, and AMPERE measurements imply that MMS observations are located on the poleward edge of the ionospheric trough where Region 2 field-aligned currents flow.

Quasi-molecular bosonic complexes-a pathway to SQUID with controlled sensitivity

NASA Astrophysics Data System (ADS)

Safavi-Naini, Arghavan; Capogrosso-Sansone, Barbara; Kuklov, Anatoly; Penna, Vittorio

2016-02-01

Recent experimental advances in realizing degenerate quantum dipolar gases in optical lattices and the flexibility of experimental setups in attaining various geometries offer the opportunity to explore exotic quantum many-body phases stabilized by anisotropic, long-range dipolar interaction. Moreover, the unprecedented control over the various physical properties of these systems, ranging from the quantum statistics of the particles, to the inter-particle interactions, allow one to engineer novel devices. In this paper, we consider dipolar bosons trapped in a stack of one-dimensional optical lattice layers, previously studied in (Safavi-Naini et al 2014 Phys. Rev. A 90 043604). Building on our prior results, we provide a description of the quantum phases stabilized in this system which include composite superfluids (CSFs), solids, and supercounterfluids, most of which are found to be threshold-less with respect to the dipolar interaction strength. We also demonstrate the effect of enhanced sensitivity to rotations of a SQUID-type device made of two CSF trapped in a ring-shaped optical lattice layer with weak links.

Colloidal Random Terpolymers: Controlling Reactivity Ratios of Colloidal Comonomers via Metal Tipping

DOE PAGES

Pavlopoulos, Nicholas G.; Dubose, Jeffrey T.; Hartnett, Erin D.; ...

2016-07-26

We report on a versatile synthetic m-shell nanoparticles (NPs) in the backbone, along with semiconductor CdSe@CdS nanorod (NR), or tetrapod (TP) side chain groups. A seven-step colloidal total synthesis enabled the synthesis of well-defined colloidal comonomers composed of a dipolar Au@CoNP attached to a single CdSe@CdS NR, or TP, where magnetic dipolar associations between Au@CoNP units promoted the formation of colloidal co- or terpolymers. The key step in this synthesis was the ability to photodeposit a single AuNP tip onto CdSe@CdS NR or TP that enables selective seeding of a dipolar CoNP onto the AuNP seed. In conclusion, we showmore » that the variation of the AuNP size directly controlled the size and dipolar character of the CoNP tip, where the size modulation of the Au and Au@CoNP tips is analogous to control of comonomer reactivity ratios in classical copolymerization processes.« less

Determining the Orientation and Localization of Membrane-Bound Peptides

PubMed Central

Hohlweg, Walter; Kosol, Simone; Zangger, Klaus

2012-01-01

Many naturally occurring bioactive peptides bind to biological membranes. Studying and elucidating the mode of interaction is often an essential step to understand their molecular and biological functions. To obtain the complete orientation and immersion depth of such compounds in the membrane or a membrane-mimetic system, a number of methods are available, which are separated in this review into four main classes: solution NMR, solid-state NMR, EPR and other methods. Solution NMR methods include the Nuclear Overhauser Effect (NOE) between peptide and membrane signals, residual dipolar couplings and the use of paramagnetic probes, either within the membrane-mimetic or in the solvent. The vast array of solid state NMR methods to study membrane-bound peptide orientation and localization includes the anisotropic chemical shift, PISA wheels, dipolar waves, the GALA, MAOS and REDOR methods and again the use of paramagnetic additives on relaxation rates. Paramagnetic additives, with their effect on spectral linewidths, have also been used in EPR spectroscopy. Additionally, the orientation of a peptide within a membrane can be obtained by the anisotropic hyperfine tensor of a rigidly attached nitroxide label. Besides these magnetic resonance techniques a series of other methods to probe the orientation of peptides in membranes has been developed, consisting of fluorescence-, infrared- and oriented circular dichroism spectroscopy, colorimetry, interface-sensitive X-ray and neutron scattering and Quartz crystal microbalance. PMID:22044140

Contrasting dynamics of electrons and protons in the near-Earth plasma sheet during dipolarization

NASA Astrophysics Data System (ADS)

Malykhin, Andrey Y.; Grigorenko, Elena E.; Kronberg, Elena A.; Koleva, Rositza; Ganushkina, Natalia Y.; Kozak, Ludmila; Daly, Patrick W.

2018-05-01

The fortunate location of Cluster and the THEMIS P3 probe in the near-Earth plasma sheet (PS) (at X ˜ -7-9 RE) allowed for the multipoint analysis of properties and spectra of electron and proton injections. The injections were observed during dipolarization and substorm current wedge formation associated with braking of multiple bursty bulk flows (BBFs). In the course of dipolarization, a gradual growth of the BZ magnetic field lasted ˜ 13 min and it was comprised of several BZ pulses or dipolarization fronts (DFs) with duration ≤ 1 min. Multipoint observations have shown that the beginning of the increase in suprathermal ( > 50 keV) electron fluxes - the injection boundary - was observed in the PS simultaneously with the dipolarization onset and it propagated dawnward along with the onset-related DF. The subsequent dynamics of the energetic electron flux was similar to the dynamics of the magnetic field during the dipolarization. Namely, a gradual linear growth of the electron flux occurred simultaneously with the gradual growth of the BZ field, and it was comprised of multiple short ( ˜ few minutes) electron injections associated with the BZ pulses. This behavior can be explained by the combined action of local betatron acceleration at the BZ pulses and subsequent gradient drifts of electrons in the flux pile up region through the numerous braking and diverting DFs. The nonadiabatic features occasionally observed in the electron spectra during the injections can be due to the electron interactions with high-frequency electromagnetic or electrostatic fluctuations transiently observed in the course of dipolarization. On the contrary, proton injections were detected only in the vicinity of the strongest BZ pulses. The front thickness of these pulses was less than a gyroradius of thermal protons that ensured the nonadiabatic acceleration of protons. Indeed, during the injections in the energy spectra of protons the pronounced bulge was clearly observed in a finite energy range ˜ 70-90 keV. This feature can be explained by the nonadiabatic resonant acceleration of protons by the bursts of the dawn-dusk electric field associated with the BZ pulses.

Development and characterization of a multi-layer magnetorheological elastomer isolator based on a Halbach array

NASA Astrophysics Data System (ADS)

Przybylski, Michal; Sun, Shuaishuai; Li, Weihua

2016-10-01

Most existing vibration isolators and dampers based on magnetorheological (MR) materials need electrical power to feed magnetic coils to stimulate the MR material, so if there is a loss of power, such as during a strong earthquake or system failure, they are unable to protect the structure. This paper outlines the design and test of a controllable multilayered magnetorheological elastomer (MRE) isolator based on a circular dipolar Halbach array; which is a set of magnets that generates a strong and uniform magnetic field. Combining an MRE layered isolator system with the Halbach array allows for constant vibration isolation with very low power consumption, where the power generated is only used to adjust the Halbach position. When this system was tested it successfully altered the lateral stiffness and damping force by 81.13% and 148.72%, respectively. This paper also includes an extended analysis of the magnetic field generated by the circular dipolar Halbach array and a discussion of the improvements that may potentially improve the range of magnetic fields generated.

Complementary p- and n-type polymer doping for ambient stable graphene inverter.

PubMed

Yun, Je Moon; Park, Seokhan; Hwang, Young Hwan; Lee, Eui-Sup; Maiti, Uday; Moon, Hanul; Kim, Bo-Hyun; Bae, Byeong-Soo; Kim, Yong-Hyun; Kim, Sang Ouk

2014-01-28

Graphene offers great promise to complement the inherent limitations of silicon electronics. To date, considerable research efforts have been devoted to complementary p- and n-type doping of graphene as a fundamental requirement for graphene-based electronics. Unfortunately, previous efforts suffer from undesired defect formation, poor controllability of doping level, and subtle environmental sensitivity. Here we present that graphene can be complementary p- and n-doped by simple polymer coating with different dipolar characteristics. Significantly, spontaneous vertical ordering of dipolar pyridine side groups of poly(4-vinylpyridine) at graphene surface can stabilize n-type doping at room-temperature ambient condition. The dipole field also enhances and balances the charge mobility by screening the impurity charge effect from the bottom substrate. We successfully demonstrate ambient stable inverters by integrating p- and n-type graphene transistors, which demonstrated clear voltage inversion with a gain of 0.17 at a 3.3 V input voltage. This straightforward polymer doping offers diverse opportunities for graphene-based electronics, including logic circuits, particularly in mechanically flexible form.

Diazo Compounds as Highly Tunable Reactants in 1,3-Dipolar Cycloaddition Reactions with Cycloalkynes†

PubMed Central

McGrath, Nicholas A.

2012-01-01

Diazo compounds, which can be accessed directly from azides by deimidogenation, are shown to be extremely versatile dipoles in 1,3-dipolar cycloaddition reactions with a cyclooctyne. The reactivity of a diazo compound can be much greater or much less than its azide analog, and is enhanced markedly in polar-protic solvents. These reactivities are predictable from frontier molecular orbital energies. The most reactive diazo compound exhibited the highest known second-order rate constant to date for a dipolar cycloaddition with a cycloalkyne. These data provide a new modality for effecting chemoselective reactions in a biological context. PMID:23227302

Polarizability extraction of complementary metamaterial elements in waveguides for aperture modeling

NASA Astrophysics Data System (ADS)

Pulido-Mancera, Laura; Bowen, Patrick T.; Imani, Mohammadreza F.; Kundtz, Nathan; Smith, David

2017-12-01

We consider the design and modeling of metasurfaces that couple energy from guided waves to propagating wave fronts. To this purpose, we develop a comprehensive, multiscale dipolar interpretation for large arrays of complementary metamaterial elements embedded in a waveguide structure. Within this modeling technique, the detailed electromagnetic response of each metamaterial element is replaced by a polarizable dipole, described by means of an effective polarizability. In this paper, we present two methods to extract this effective polarizability. The first method invokes surface equivalence principles, averaging over the effective surface currents and charges induced in the element's surface in order to obtain the effective dipole moments, from which the effective polarizability can be inferred. The second method is based in the coupled-mode theory, from which a direct relationship between the effective polarizability and the amplitude coefficients of the scattered waves can be deduced. We demonstrate these methods on several variants of waveguide-fed metasurface elements (both one- and two-dimensional waveguides), finding excellent agreement between the two, as well as with the analytical expressions derived for circular and elliptical irises. With the effective polarizabilities of the metamaterial elements accurately determined, the radiated fields generated by a waveguide-fed metasurface can be found self-consistently by including the interactions between polarizable dipoles. The dipole description provides an effective perspective and computational framework for engineering metasurface structures such as holograms, lenses, and beam-forming arrays, among others.

RDC-enhanced structure calculation of a β-heptapeptide in methanol.

PubMed

Rigling, Carla; Ebert, Marc-Olivier

2017-07-01

Residual dipolar couplings (RDCs) are a rich source of structural information that goes beyond the range covered by the nuclear Overhauser effect or scalar coupling constants. They can only be measured in partially oriented samples. RDC studies of peptides in organic solvents have so far been focused on samples in chloroform or DMSO. Here, we show that stretched poly(vinyl acetate) can be used for the partial alignment of a linear β-peptide with proteinogenic side chains in methanol. 1 D CH , 1 D NH , and 2 D HH RDCs were collected with this sample and included as restraints in a simulated annealing calculation. Incorporation of RDCs in the structure calculation process improves the long-range definition in the backbone of the resulting 3 14 -helix and uncovers side-chain mobility. Experimental side-chain RDCs of the central leucine and valine residues are in good agreement with predicted values from a local three-state model. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Aromatic Polythiourea Dielectrics with High Energy Density, High Breakdown Strength, and Low Dielectric Loss

NASA Astrophysics Data System (ADS)

Wu, Shan; Burlingame, Quinn; Lin, Minren; Zhang, Qiming

2013-03-01

There is an increasing demand on dielectric materials with high electric energy density and low loss for a broad range of applications in modern electronics and electrical power systems such as hybrid electric vehicles (HEV), medical defibrillators, filters, and switched-mode power supplies. One major challenge in developing dielectric polymers is how to achieve high energy density Ue while maintaining low dielectric loss, even at very high-applied electric fields. Here we show that amorphous polar-polymers with very low impurity concentration can be promising for realizing such a dielectric polymer. Polar-polymer with high dipole moment and weak dipole coupling can provide relatively high dielectric constant for high Ue, eliminate polarization and conduction losses due to weak dipolar coupling and strong polar-scattering to charge carriers. Indeed, an aromatic polythiourea thin film can maintain low loss to high fields (>1 GV/m) with a high Ue (~ 24 J/cm3) , which is very attractive for energy storage capacitors.

Novel insights into the mechanism of the ortho/para spin conversion of hydrogen pairs: implications for catalysis and interstellar water.

PubMed

Limbach, Hans-Heinrich; Buntkowsky, Gerd; Matthes, Jochen; Gründemann, Stefan; Pery, Tal; Walaszek, Bernadeta; Chaudret, Bruno

2006-03-13

The phenomenon of exchange coupling is taken into account in the description of the magnetic nuclear spin conversion between bound ortho- and para-dihydrogen. This conversion occurs without bond breaking, in contrast to the chemical spin conversion. It is shown that the exchange coupling needs to be reduced so that the corresponding exchange barrier can increase and the given magnetic interaction can effectively induce a spin conversion. The implications for related molecules such as water are discussed. For ice, a dipolar magnetic conversion and for liquid water a chemical conversion are predicted to occur within the millisecond timescale. It follows that a separation of water into its spin isomers, as proposed by Tikhonov and Volkov (Science 2002, 296, 2363), is not feasible. Nuclear spin temperatures of water vapor in comets, which are smaller than the gas-phase equilibrium temperatures, are proposed to be diagnostic for the temperature of the ice or the dust surface from which the water was released.

Relation between native ensembles and experimental structures of proteins

PubMed Central

Best, Robert B.; Lindorff-Larsen, Kresten; DePristo, Mark A.; Vendruscolo, Michele

2006-01-01

Different experimental structures of the same protein or of proteins with high sequence similarity contain many small variations. Here we construct ensembles of “high-sequence similarity Protein Data Bank” (HSP) structures and consider the extent to which such ensembles represent the structural heterogeneity of the native state in solution. We find that different NMR measurements probing structure and dynamics of given proteins in solution, including order parameters, scalar couplings, and residual dipolar couplings, are remarkably well reproduced by their respective high-sequence similarity Protein Data Bank ensembles; moreover, we show that the effects of uncertainties in structure determination are insufficient to explain the results. These results highlight the importance of accounting for native-state protein dynamics in making comparisons with ensemble-averaged experimental data and suggest that even a modest number of structures of a protein determined under different conditions, or with small variations in sequence, capture a representative subset of the true native-state ensemble. PMID:16829580

Multiple-quantum spin counting in magic-angle-spinning NMR via low-power symmetry-based dipolar recoupling

NASA Astrophysics Data System (ADS)

Teymoori, Gholamhasan; Pahari, Bholanath; Viswanathan, Elumalai; Edén, Mattias

2013-11-01

By using a symmetry-based R281R28-1 double-quantum (2Q) dipolar recoupling sequence, we demonstrate high-order multiple-quantum coherence (MQC) excitation at fast magic-angle spinning (MAS) frequencies up to 34 kHz. This scheme combines several attractive features, such as a relatively high dipolar scaling factor, good compensation to rf-errors, isotropic and anisotropic chemical shifts, as well as an ultra-low radio-frequency (rf) power requirement. The latter translates into nutation frequencies below 30 kHz for MAS rates up to 60 kHz, thereby permitting rf application for very long excitation periods without risk of damaging the NMR probehead or sample, while the compensation to chemical shifts improves as the MAS rate increases. 31P MQC spin counting is demonstrated on powders of calcium hydroxyapatite (Ca5(PO4)3OH) and anhydrous sodium diphosphate (Na4P2O7), from which all even coherence orders up to 30 and 14 were detected, respectively, over the respective MAS ranges of 15-24 kHz and 20-34 kHz. The amplitude distributions among the 31P MQC orders depend on the precise nutation frequency during recoupling, despite that the highest detected order was relatively insensitive to this parameter. An observed gradual transition from a Gaussian to exponential functionality of the MQC amplitude-profile is discussed in relation to the prevailing approach to derive spin-cluster sizes by fitting the MQC amplitude-distribution to a Gaussian decay, where minor systematic deviations between the model and experimental data are frequently reported.

A Dipolar Anthracene Dye: Synthesis, Optical Properties and Two-photon Tissue Imaging.

PubMed

Moon, Hyunsoo; Jun, Yong Woong; Kim, Dokyoung; Ryu, Hye Gun; Wang, Taejun; Kim, Ki Hean; Huh, Youngbuhm; Jung, Junyang; Ahn, Kyo Han

2016-09-20

Two-photon microscopy is a powerful tool for studying biological systems. In search of novel two-photon absorbing dyes for bioimaging, we synthesized a new anthracene-based dipolar dye (anthradan) and evaluated its two-photon absorbing and imaging properties. The new anthradan, 9,10-bis(o-dimethoxy-phenyl)-anthradan, absorbs and emits at longer wavelengths than acedan, a well-known two-photon absorbing dye. It is also stable under two-photon excitation conditions and biocompatible, and thus used for two-photon imaging of mouse organ tissues to show bright, near-red fluorescence along with negligible autofluorescence. Such an anthradan thus holds promise as a new class of two-photon absorbing dyes for the development of fluorescent probes and tags for biological systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Motional studies of one and two laser-cooled trapped ions for electric-field sensing applications

NASA Astrophysics Data System (ADS)

Domínguez, F.; Gutiérrez, M. J.; Arrazola, I.; Berrocal, J.; Cornejo, J. M.; Del Pozo, J. J.; Rica, R. A.; Schmidt, S.; Solano, E.; Rodríguez, D.

2018-03-01

We have studied the dynamics of one and two laser-cooled trapped ?Ca? ions by applying electric fields of different nature along the axial direction of the trap, namely, driving the motion with a harmonic dipolar field, or with white noise. These two types of driving induce distinct motional states of the axial modes: a coherent oscillation with the dipolar field, or an enhanced Brownian motion due to an additional contribution to the heating rate from the electric noise. In both scenarios, the sensitivity of an isolated ion and a laser-cooled two-ion crystal has been evaluated and compared. The analysis and understanding of this dynamics is important towards the implementation of a novel Penning trap mass-spectroscopy technique based on optical detection, aiming at improving precision and sensitivity.

All-dielectric perforated metamaterials with toroidal dipolar response (Conference Presentation)

NASA Astrophysics Data System (ADS)

Stenishchev, Ivan; Basharin, Alexey A.

2017-05-01

We present metamaterials based on dielectric slab with perforated identical cylindrical clusters with perforated holes, which allow to support the toroidal dipolar response due to Mie-resonances in each hole. Note that proposed metamaterial is technologically simple for fabrication in optical frequency range. Metamaterial can be fabricated by several methods. For instance, we may apply the molecular beam epitaxy method for deposition of Si or GaAs layers, which have permittivity close to 16. Next step, nanometer/micrometer holes are perforated by focused ion beam method or laser cutting method. Fundamental difference of proposed metamaterial is technological fabrication process. Classically all- dielectric optical metamaterials consist of nano-spheres or nano-discs, which are complicated for fabrication, while our idea and suggested metamaterials are promising prototype of various optical/THz all-dielectic devices as sensor, nano-antennas elements for nanophotonics.

Unveiling Inherent Degeneracies in Determining Population-weighted Ensembles of Inter-domain Orientational Distributions Using NMR Residual Dipolar Couplings: Application to RNA Helix Junction Helix Motifs

PubMed Central

Yang, Shan; Al-Hashimi, Hashim M.

2016-01-01

A growing number of studies employ time-averaged experimental data to determine dynamic ensembles of biomolecules. While it is well known that different ensembles can satisfy experimental data to within error, the extent and nature of these degeneracies, and their impact on the accuracy of the ensemble determination remains poorly understood. Here, we use simulations and a recently introduced metric for assessing ensemble similarity to explore degeneracies in determining ensembles using NMR residual dipolar couplings (RDCs) with specific application to A-form helices in RNA. Various target ensembles were constructed representing different domain-domain orientational distributions that are confined to a topologically restricted (<10%) conformational space. Five independent sets of ensemble averaged RDCs were then computed for each target ensemble and a ‘sample and select’ scheme used to identify degenerate ensembles that satisfy RDCs to within experimental uncertainty. We find that ensembles with different ensemble sizes and that can differ significantly from the target ensemble (by as much as ΣΩ ~ 0.4 where ΣΩ varies between 0 and 1 for maximum and minimum ensemble similarity, respectively) can satisfy the ensemble averaged RDCs. These deviations increase with the number of unique conformers and breadth of the target distribution, and result in significant uncertainty in determining conformational entropy (as large as 5 kcal/mol at T = 298 K). Nevertheless, the RDC-degenerate ensembles are biased towards populated regions of the target ensemble, and capture other essential features of the distribution, including the shape. Our results identify ensemble size as a major source of uncertainty in determining ensembles and suggest that NMR interactions such as RDCs and spin relaxation, on their own, do not carry the necessary information needed to determine conformational entropy at a useful level of precision. The framework introduced here provides a general approach for exploring degeneracies in ensemble determination for different types of experimental data. PMID:26131693

Spatial reorientation experiments for NMR of solids and partially oriented liquids.

PubMed

Martin, Rachel W; Kelly, John E; Collier, Kelsey A

2015-11-01

Motional reorientation experiments are extensions of Magic Angle Spinning (MAS) where the rotor axis is changed in order to average out, reintroduce, or scale anisotropic interactions (e.g. dipolar couplings, quadrupolar interactions or chemical shift anisotropies). This review focuses on Variable Angle Spinning (VAS), Switched Angle Spinning (SAS), and Dynamic Angle Spinning (DAS), all of which involve spinning at two or more different angles sequentially, either in successive experiments or during a multidimensional experiment. In all of these experiments, anisotropic terms in the Hamiltonian are scaled by changing the orientation of the spinning sample relative to the static magnetic field. These experiments vary in experimental complexity and instrumentation requirements. In VAS, many one-dimensional spectra are collected as a function of spinning angle. In SAS, dipolar couplings and/or chemical shift anisotropies are reintroduced by switching the sample between two different angles, often 0° or 90° and the magic angle, yielding a two-dimensional isotropic-anisotropic correlation spectrum. Dynamic Angle Spinning (DAS) is a related experiment that is used to simultaneously average out the first- and second-order quadrupolar interactions, which cannot be accomplished by spinning at any unique rotor angle in physical space. Although motional reorientation experiments generally require specialized instrumentation and data analysis schemes, some are accessible with only minor modification of standard MAS probes. In this review, the mechanics of each type of experiment are described, with representative examples. Current and historical probe and coil designs are discussed from the standpoint of how each one accomplishes the particular objectives of the experiment(s) it was designed to perform. Finally, applications to inorganic materials and liquid crystals, which present very different experimental challenges, are discussed. The review concludes with perspectives on how motional reorientation experiments can be applied to current problems in chemistry, molecular biology, and materials science, given the many advances in high-field NMR magnets, fast spinning, and sample preparation realized in recent years. Copyright © 2015 Elsevier B.V. All rights reserved.

Protein addressing on patterned microchip by coupling chitosan electrodeposition and 'electro-click' chemistry.

PubMed

Shi, Xiao-Wen; Qiu, Ling; Nie, Zhen; Xiao, Ling; Payne, Gregory F; Du, Yumin

2013-12-01

Many applications in proteomics and lab-on-chip analysis require methods that guide proteins to assemble at surfaces with high spatial and temporal control. Electrical inputs are particularly convenient to control, and there has been considerable effort to discover simple and generic mechanisms that allow electrical inputs to trigger protein assembly on-demand. Here, we report the electroaddressing of a protein to a patterned surface by coupling two generic electroaddressing mechanisms. First, we electrodeposit the stimuli-responsive film-forming aminopolysaccharide chitosan to form a hydrogel matrix at the electrode surface. After deposition, the matrix is chemically functionalized with alkyne groups. Second, we ''electro-click' an azide-tagged protein to the functionalized matrix using electrical signals to trigger conjugation by Huisgen 1,3-dipolar cycloadditions. Specifically, a cathodic potential is applied to the matrix-coated electrode to reduce Cu(II) to Cu(I) which is required for the click reaction. Using fluorescently-labeled bovine serum albumin as our model, we demonstrate that protein conjugation can be controlled spatially and temporally. We anticipate that the coupling of polysaccharide electrodeposition and electro-click chemistry will provide a simple and generic approach to electroaddress proteins within compatible hydrogel matrices.

Electric Dipolar Kondo Effect Emerging from a Vibrating Magnetic Ion

NASA Astrophysics Data System (ADS)

Hotta, Takashi; Ueda, Kazuo

2012-06-01

When a magnetic ion vibrates in a metal, it inevitably introduces a new channel of hybridization with conduction electrons, and in general, the vibrating ion induces an electric dipole moment. In such a situation, we find that magnetic and nonmagnetic Kondo effects alternatively occur due to the screening of the spin moment and electric dipole moment of the vibrating ion. In particular, the electric dipolar two-channel Kondo effect is found to occur for a weak Coulomb interaction. We also show that a magnetically robust heavy-electron state appears near the fixed point of the electric dipolar two-channel Kondo effect. We believe that the vibrating magnetic ion opens a new door in Kondo physics.

Ionic-liquid-induced ferroelectric polarization in poly(vinylidene fluoride) thin films

NASA Astrophysics Data System (ADS)

Wang, Feipeng; Lack, Alexander; Xie, Zailai; Frübing, Peter; Taubert, Andreas; Gerhard, Reimund

2012-02-01

Thin films of ferroelectric β-phase poly(vinylidene fluoride) (PVDF) were spin-coated from a solution that contained small amounts of the ionic liquid (IL) 1-ethyl-3-methylimidazolium nitrate. A remanent polarization of 60 mC/m2 and a quasi-static pyroelectric coefficient of 19 μC/m2K at 30 °C were observed in the films. It is suggested that the IL promotes the formation of the β phase through dipolar interactions between PVDF chain-molecules and the IL. The dipolar interactions are identified as Coulomb attraction between hydrogen atoms in PVDF chains and anions in IL. The strong crystallinity increase is probably caused by the same dipolar interaction as well.

Dipolar and spinor bosonic systems

NASA Astrophysics Data System (ADS)

Yukalov, V. I.

2018-05-01

The main properties and methods of describing dipolar and spinor atomic systems, composed of bosonic atoms or molecules, are reviewed. The general approach for the correct treatment of Bose-condensed atomic systems with nonlocal interaction potentials is explained. The approach is applied to Bose-condensed systems with dipolar interaction potentials. The properties of systems with spinor interaction potentials are described. Trapped atoms and atoms in optical lattices are considered. Effective spin Hamiltonians for atoms in optical lattices are derived. The possibility of spintronics with cold atom is emphasized. The present review differs from the previous review articles by concentrating on a thorough presentation of basic theoretical points, helping the reader to better follow mathematical details and to make clearer physical conclusions.

A Bayesian Approach for Determining Protein Side-Chain Rotamer Conformations Using Unassigned NOE Data

PubMed Central

Zeng, Jianyang; Roberts, Kyle E.; Zhou, Pei

2011-01-01

Abstract A major bottleneck in protein structure determination via nuclear magnetic resonance (NMR) is the lengthy and laborious process of assigning resonances and nuclear Overhauser effect (NOE) cross peaks. Recent studies have shown that accurate backbone folds can be determined using sparse NMR data, such as residual dipolar couplings (RDCs) or backbone chemical shifts. This opens a question of whether we can also determine the accurate protein side-chain conformations using sparse or unassigned NMR data. We attack this question by using unassigned nuclear Overhauser effect spectroscopy (NOESY) data, which records the through-space dipolar interactions between protons nearby in three-dimensional (3D) space. We propose a Bayesian approach with a Markov random field (MRF) model to integrate the likelihood function derived from observed experimental data, with prior information (i.e., empirical molecular mechanics energies) about the protein structures. We unify the side-chain structure prediction problem with the side-chain structure determination problem using unassigned NMR data, and apply the deterministic dead-end elimination (DEE) and A* search algorithms to provably find the global optimum solution that maximizes the posterior probability. We employ a Hausdorff-based measure to derive the likelihood of a rotamer or a pairwise rotamer interaction from unassigned NOESY data. In addition, we apply a systematic and rigorous approach to estimate the experimental noise in NMR data, which also determines the weighting factor of the data term in the scoring function derived from the Bayesian framework. We tested our approach on real NMR data of three proteins: the FF Domain 2 of human transcription elongation factor CA150 (FF2), the B1 domain of Protein G (GB1), and human ubiquitin. The promising results indicate that our algorithm can be applied in high-resolution protein structure determination. Since our approach does not require any NOE assignment, it can accelerate the NMR structure determination process. PMID:21970619

Optimized coupling of cold atoms into a fiber using a blue-detuned hollow-beam funnel

NASA Astrophysics Data System (ADS)

Poulin, Jerome; Light, Philip S.; Kashyap, Raman; Luiten, Andre N.

2011-11-01

We theoretically investigate the process of coupling cold atoms into the core of a hollow-core photonic-crystal optical fiber using a blue-detuned Laguerre-Gaussian beam. In contrast to the use of a red-detuned Gaussian beam to couple the atoms, the blue-detuned hollow beam can confine cold atoms to the darkest regions of the beam, thereby minimizing shifts in the internal states and making the guide highly robust to heating effects. This single optical beam is used as both a funnel and a guide to maximize the number of atoms into the fiber. In the proposed experiment, Rb atoms are loaded into a magneto-optical trap (MOT) above a vertically oriented optical fiber. We observe a gravito-optical trapping effect for atoms with high orbital momentum around the trap axis, which prevents atoms from coupling to the fiber: these atoms lack the kinetic energy to escape the potential and are thus trapped in the laser funnel indefinitely. We find that by reducing the dipolar force to the point at which the trapping effect just vanishes, it is possible to optimize the coupling of atoms into the fiber. Our simulations predict that by using a low-power (2.5 mW) and far-detuned (300 GHz) Laguerre-Gaussian beam with a 20-μm-radius core hollow fiber, it is possible to couple 11% of the atoms from a MOT 9 mm away from the fiber. When the MOT is positioned farther away, coupling efficiencies over 50% can be achieved with larger core fibers.

The Role of the Upper Atmosphere for Dawn-Dusk and Interhemispheric Differences in the Coupled Magnetosphere-Ionosphere-Thermosphere System

NASA Astrophysics Data System (ADS)

Foerster, M.; Doornbos, E.; Haaland, S.

2016-12-01

Solar wind and IMF interaction with the geomagnetic field sets up a large-scale plasma circulation in the Earth's magnetosphere and the magnetically tightly connected ionosphere. The ionospheric ExB ion drift at polar latitudes accelerates the neutral gas as a nondivergent momentum source primarily in force balance with pressure gradients, while the neutral upper thermosphere circulation is essentially modified by apparent forces due to Earth's rotation (Coriolis and centrifugal forces) as well as advection and viscous forces. The apparent forces affect the dawn and dusk side asymmetrically, favouring a large dusk-side neutral wind vortex, while the non-dipolar portions of the Earth's magnetic field constitute significant hemispheric differences in magnetic flux and field configurations that lead to essential interhemispheric differences of the ion-neutral interaction. We present statistical studies of both the high-latitude ionospheric convection and the upper thermospheric circulation patterns based on measurements of the electron drift instrument (EDI) on board the Cluster satellites and by the accelerometer on board the CHAMP, GOCE, and Swarm spacecraft, respectively.

Ferromagnetic Swimmers - Devices and Applications

NASA Astrophysics Data System (ADS)

Hamilton, Joshua; Petrov, Peter; Winlove, C. Peter; Gilbert, Andrew; Bryan, Matthew; Ogrin, Feodor

2017-11-01

Microscopic swimming devices hold promise for radically new applications in lab-on-a-chip and microfluidic technology, diagnostics and drug delivery etc. We propose a new class of autonomous ferromagnetic swimming devices, actuated and controlled solely by an oscillating magnetic field. Experimentally, these devices (3.6 mm) are based on a pair of interacting ferromagnetic particles of different size and different anisotropic properties joined by an elastic link and actuated by an external time-dependent magnetic field. The net motion is generated through a combination of dipolar interparticle gradient forces, time-dependent torque and hydrodynamic coupling. We investigate the dynamic performance of a prototype (3.6 mm) of the ferromagnetic swimmer in fluids of different viscosity as a function of the external field parameters and demonstrate stable propulsion over a wide range of Reynolds numbers. Manipulation of the external magnetic field resulted in robust control over the speed and direction of propulsion. We also demonstrate our ferromagnetic swimmer working as a macroscopic prototype of a microfluidic pump. By physically tethering the swimmer, instead of swimming, the swimmer generates a directional flow of liquid around itself.

Investigation of head group behaviour of lamellar liquid crystals

NASA Astrophysics Data System (ADS)

Delikatny, E. J.; Burnell, E. E.

A mean field equilibrium statistical mechanical model, based on the Samulski inertial frame model, was developed to simulate experimental dipolar and quadrupolar nmr couplings of isotopically substituted potassium palmitates. An isolated four spin system was synthesized (2,2,3,3,-H4-palmitic acid-d27) and in conjunction with data presented in a previous paper on perdeuterated and carbon 13 labelled soaps, the head group behaviour of the molecule was investigated. Two interactions were considered in the modelling procedure: a mean field steric interaction characterized by a constraining cylinder, and a head group interaction characterized by a mass on the end of a rod of variable length. The rod lies along the first C-C bond direction and accounts for the interaction between polar head group and water via its effect on the moment of inertia of the molecule. In potassium palmitate mean field steric repulsive forces remain constant over the entire temperature range studied. In contrast, electrostatic interactions between polar head group and water, approximately constant at higher temperatures, increase dramatically as the phase transition is approached. This evidence supports a previously proposed model of lipidwater interaction.

AssignFit: a program for simultaneous assignment and structure refinement from solid-state NMR spectra

PubMed Central

Tian, Ye; Schwieters, Charles D.; Opella, Stanley J.; Marassi, Francesca M.

2011-01-01

AssignFit is a computer program developed within the XPLOR-NIH package for the assignment of dipolar coupling (DC) and chemical shift anisotropy (CSA) restraints derived from the solid-state NMR spectra of protein samples with uniaxial order. The method is based on minimizing the difference between experimentally observed solid-state NMR spectra and the frequencies back calculated from a structural model. Starting with a structural model and a set of DC and CSA restraints grouped only by amino acid type, as would be obtained by selective isotopic labeling, AssignFit generates all of the possible assignment permutations and calculates the corresponding atomic coordinates oriented in the alignment frame, together with the associated set of NMR frequencies, which are then compared with the experimental data for best fit. Incorporation of AssignFit in a simulated annealing refinement cycle provides an approach for simultaneous assignment and structure refinement (SASR) of proteins from solid-state NMR orientation restraints. The methods are demonstrated with data from two integral membrane proteins, one α-helical and one β-barrel, embedded in phospholipid bilayer membranes. PMID:22036904

Complex Dipolar Matter

DTIC Science & Technology

2014-11-10

opportunities for advanced material development and quantum simulators. These molecules include (1) the already quantum degenerate bi- alkali singlet sigma...case potassium-rubidium (KRb) and related molecules; (2) opto-electrically trapped symmetric top molecules soon to reach quantum degeneracy and...rubidium; (C) a correction of phase diagrams for dipolar gases necessary to understand experimental measurements and build accurate quantum simulators

Topological defect formation in rotating binary dipolar Bose–Einstein condensate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xiao-Fei, E-mail: xfzhang@ntsc.ac.cn; University of Chinese Academy of Sciences, Beijing 100049; Department of Engineering Science, University of Electro-Communications, Tokyo 182-8585

We investigate the topological defects and spin structures of a rotating binary Bose–Einstein condensate, which consists of both dipolar and scalar bosonic atoms confined in spin-dependent optical lattices, for an arbitrary orientation of the dipoles with respect to their plane of motion. Our results show that the tunable dipolar interaction, especially the orientation of the dipoles, can be used to control the direction of stripe phase and its related half-vortex sheets. In addition, it can also be used to obtain a regular arrangement of various topological spin textures, such as meron, circular and cross disgyration spin structures. We point outmore » that such topological defects and regular arrangement of spin structures arise primarily from the long-range and anisotropic nature of dipolar interaction and its competition with the spin-dependent optical lattices and rotation. - Highlights: • Effects of both strength and orientation of the dipoles are discussed. • Various topological defects can be formed in different parameter regions. • Present one possible way to obtain regular arrangements of spin textures.« less

Random acoustic metamaterial with a subwavelength dipolar resonance.

PubMed

Duranteau, Mickaël; Valier-Brasier, Tony; Conoir, Jean-Marc; Wunenburger, Régis

2016-06-01

The effective velocity and attenuation of longitudinal waves through random dispersions of rigid, tungsten-carbide beads in an elastic matrix made of epoxy resin in the range of beads volume fraction 2%-10% are determined experimentally. The multiple scattering model proposed by Luppé, Conoir, and Norris [J. Acoust. Soc. Am. 131(2), 1113-1120 (2012)], which fully takes into account the elastic nature of the matrix and the associated mode conversions, accurately describes the measurements. Theoretical calculations show that the rigid particles display a local, dipolar resonance which shares several features with Minnaert resonance of bubbly liquids and with the dipolar resonance of core-shell particles. Moreover, for the samples under study, the main cause of smoothing of the dipolar resonance of the scatterers and the associated variations of the effective mass density of the dispersions is elastic relaxation, i.e., the finite time required for the shear stresses associated to the translational motion of the scatterers to propagate through the matrix. It is shown that its influence is governed solely by the value of the particle to matrix mass density contrast.

The effect of bottom friction on tidal dipolar vortices and the associated transport

NASA Astrophysics Data System (ADS)

Duran-Matute, Matias; Kamp, Leon; van Heijst, Gertjan

2016-11-01

Tidal dipolar vortices can be formed in a semi-enclosed basin as the tides flow in and out through an inlet. If they are strong enough to overcome the opposing tidal currents, these vortices can travel away from the inlet due to their self-propelling mechanism, and hence, act as an efficient transport agent for suspended material. We present results of two-dimensional numerical simulations of the flow through an idealized tidal inlet, with either a linear or a nonlinear parameterization of the bottom friction. We then quantify the effect of the bottom friction on the propagation of the dipolar vortex and on its ability as a transport agent by computing the flushing and residence times of passive particles. Bottom friction is detrimental to the ability of tidal dipolar vortices to propagate and hinders transport away from the inlet. The magnitude of this effect is related to the relative duration of the tidal period as compared to the typical decay time scale of the vortex dipole. This research is funded by NWO (the Netherlands) through the VENI Grant 863.13.022.

Quantum spin ices and magnetic states from dipolar-octupolar doublets on the pyrochlore lattice

NASA Astrophysics Data System (ADS)

Chen, Gang

We consider a class of electron systems in which dipolar-octupolar Kramers doublets arise on the pyrochlore lattice. In the localized limit, the Kramers doublets are described by the effective spin 1/2 pseudospins. The most general nearest-neighbor exchange model between these pseudospins is the XYZ model. In additional to dipolar ordered and octupolar ordered magnetic states, we show that this XYZ model exhibits two distinct quantum spin ice (QSI) phases, that we dub dipolar QSI and octupolar QSI. These two QSIs are distinct symmetry enriched U(1) quantum spin liquids, enriched by the lattice symmetry. Moreover, the XYZ model is absent from the notorious sign problem for a quantum Monte Carlo simulation in a large parameter space. We discuss the potential relevance to real material systems such as Dy2Ti2O7, Nd2Zr2O7, Nd2Hf2O7, Nd2Ir2O7, Nd2Sn2O7 and Ce2Sn2O7. chggst@gmail.com, Refs: Y-P Huang, G Chen, M Hermele, Phys. Rev. Lett. 112, 167203 (2014).

The 3D Kasteleyn transition in dipolar spin ice: a numerical study with the conserved monopoles algorithm

NASA Astrophysics Data System (ADS)

Baez, M. L.; Borzi, R. A.

2017-02-01

We study the three-dimensional Kasteleyn transition in both nearest neighbours and dipolar spin ice models using an algorithm that conserves the number of excitations. We first limit the interactions range to nearest neighbours to test the method in the presence of a field applied along ≤ft[1 0 0\\right] , and then focus on the dipolar spin ice model. The effect of dipolar interactions, which is known to be greatly self screened at zero field, is particularly strong near full polarization. It shifts the Kasteleyn transition to lower temperatures, which decreases  ≈0.4 K for the parameters corresponding to the best known spin ice materials, \\text{D}{{\\text{y}}2}\\text{T}{{\\text{i}}2}{{\\text{O}}7} and \\text{H}{{\\text{o}}2}\\text{T}{{\\text{i}}2}{{\\text{O}}7} . This shift implies effective dipolar fields as big as 0.05 T opposing the applied field, and thus favouring the creation of ‘strings’ of reversed spins. We compare the reduction in the transition temperature with results in previous experiments, and study the phenomenon quantitatively using a simple molecular field approach. Finally, we relate the presence of the effective residual field to the appearance of string-ordered phases at low fields and temperatures, and we check numerically that for fields applied along ≤ft[1 0 0\\right] there are only three different stable phases at zero temperature.

Condensation to a strongly correlated dark fluid of two dimensional dipolar excitons

NASA Astrophysics Data System (ADS)

Mazuz-Harpaz, Yotam; Cohen, Kobi; Rapaport, Ronen

2017-08-01

Recently we reported on the condensation of cold, electrostatically trapped dipolar excitons in GaAs bilayer heterostructure into a new, dense and dark collective phase. Here we analyze and discuss in detail the experimental findings and the emerging evident properties of this collective liquid-like phase. We show that the phase transition is characterized by a sharp increase of the number of non-emitting dipoles, by a clear contraction of the fluid spatial extent into the bottom of the parabolic-like trap, and by spectral narrowing. We extract the total density of the condensed phase which we find to be consistent with the expected density regime of a quantum liquid. We show that there are clear critical temperature and excitation power onsets for the phase transition and that as the power further increases above the critical power, the strong darkening is reduced down until no clear darkening is observed. At this point another transition appears which we interpret as a transition to a strongly repulsive yet correlated e-h plasma. Based on the experimental findings, we suggest that the physical mechanism that may be responsible for the transition is a dynamical final-state stimulation of the dipolar excitons to their dark spin states, which have a long lifetime and thus support the observed sharp increase in density. Further experiments and modeling will hopefully be able to unambiguously identify the physical mechanism behind these recent observations.

Longitudinal nuclear spin relaxation of ortho- and para-hydrogen dissolved in organic solvents.

PubMed

Aroulanda, Christie; Starovoytova, Larisa; Canet, Daniel

2007-10-25

The longitudinal relaxation time of ortho-hydrogen (the spin isomer directly observable by NMR) has been measured in various organic solvents as a function of temperature. Experimental data are perfectly interpreted by postulating two mechanisms, namely intramolecular dipolar interaction and spin-rotation, with activation energies specific to these two mechanisms and to the solvent in which hydrogen is dissolved. This permits a clear separation of the two contributions at any temperature. Contrary to the self-diffusion coefficients at a given temperature, the rotational correlation times extracted from the dipolar relaxation contribution do not exhibit any definite trend with respect to solvent viscosity. Likewise, the spin-rotation correlation time obeys Hubbard's relation only in the case of hydrogen dissolved in acetone-d6, yielding in that case a spin-rotation constant in agreement with literature data. Concerning para-hydrogen, which is NMR-silent, the only feasible approach is to dissolve para-enriched hydrogen in these solvents and to follow the back-conversion of the para-isomer into the ortho-isomer. Experimentally, this conversion has been observed to be exponential, with a time constant assumed to be the relaxation time of the singlet state (the spin state of the para-isomer). A theory, based on intermolecular dipolar interactions, has been worked out for explaining the very large values of these relaxation times which appear to be solvent-dependent.

Near-field investigation of the effect of the array edge on the resonance of loop frequency selective surface elements at mid-infrared wavelengths.

PubMed

Tucker, Eric; D' Archangel, Jeffrey; Raschke, Markus B; Boreman, Glenn

2015-05-04

Mid-infrared scattering scanning near-field optical microscopy, in combination with far-field infrared spectroscopy, and simulations, was employed to investigate the effect of mutual-element coupling towards the edge of arrays of loop elements acting as frequency selective surfaces (FSSs). Two different square loop arrays on ZnS over a ground plane, resonant at 10.3 µm, were investigated. One array had elements that were closely spaced while the other array had elements with greater inter-element spacing. In addition to the dipolar resonance, we observed a new emergent resonance associated with the edge of the closely-spaced array as a finite size effect, due to the broken translational invariance.

Janus and Huygens Dipoles: Near-Field Directionality Beyond Spin-Momentum Locking.

PubMed

Picardi, Michela F; Zayats, Anatoly V; Rodríguez-Fortuño, Francisco J

2018-03-16

Unidirectional scattering from circularly polarized dipoles has been demonstrated in near-field optics, where the quantum spin-Hall effect of light translates into spin-momentum locking. By considering the whole electromagnetic field, instead of its spin component alone, near-field directionality can be achieved beyond spin-momentum locking. This unveils the existence of the Janus dipole, with side-dependent topologically protected coupling to waveguides, and reveals the near-field directionality of Huygens dipoles, generalizing Kerker's condition. Circular dipoles, together with Huygens and Janus sources, form the complete set of all possible directional dipolar sources in the far- and near-field. This allows the designing of directional emission, scattering, and waveguiding, fundamental for quantum optical technology, integrated nanophotonics, and new metasurface designs.

Janus and Huygens Dipoles: Near-Field Directionality Beyond Spin-Momentum Locking

NASA Astrophysics Data System (ADS)

Picardi, Michela F.; Zayats, Anatoly V.; Rodríguez-Fortuño, Francisco J.

2018-03-01

Unidirectional scattering from circularly polarized dipoles has been demonstrated in near-field optics, where the quantum spin-Hall effect of light translates into spin-momentum locking. By considering the whole electromagnetic field, instead of its spin component alone, near-field directionality can be achieved beyond spin-momentum locking. This unveils the existence of the Janus dipole, with side-dependent topologically protected coupling to waveguides, and reveals the near-field directionality of Huygens dipoles, generalizing Kerker's condition. Circular dipoles, together with Huygens and Janus sources, form the complete set of all possible directional dipolar sources in the far- and near-field. This allows the designing of directional emission, scattering, and waveguiding, fundamental for quantum optical technology, integrated nanophotonics, and new metasurface designs.

Bogolon-mediated electron capture by impurities in hybrid Bose-Fermi systems

NASA Astrophysics Data System (ADS)

Boev, M. V.; Kovalev, V. M.; Savenko, I. G.

2018-04-01

We investigate the processes of electron capture by a Coulomb impurity center residing in a hybrid system consisting of spatially separated two-dimensional layers of electron and Bose-condensed dipolar exciton gases coupled via the Coulomb forces. We calculate the probability of the electron capture accompanied by the emission of a single Bogoliubov excitation (bogolon), similar to regular phonon-mediated scattering in solids. Furthermore, we study the electron capture mediated by the emission of a pair of bogolons in a single capture event and show that these processes not only should be treated in the same order of the perturbation theory, but also they give a more important contribution than single-bogolon-mediated capture, in contrast with regular phonon scattering.

Solution structure of lysine-free (K0) ubiquitin

PubMed Central

Huang, Tao; Li, Jess; Byrd, R Andrew

2014-01-01

Lysine-free ubiquitin (K0-Ub) is commonly used to study the ubiquitin-signaling pathway, where it is assumed to have the same structure and function as wild-type ubiquitin (wt-Ub). However, the K0-Ub 15N heteronuclear single quantum correlation NMR spectrum differs significantly from wt-Ub and the melting temperature is depressed by 19°C, raising the question of the structural integrity and equivalence to wt-Ub. The three-dimensional structure of K0-Ub was determined by solution NMR, using chemical shift and residual dipolar coupling data. K0-Ub adopts the same backbone structure as wt-Ub, and all significant chemical shifts can be related to interactions impacted by the K to R mutations. PMID:24591328

Origin of SMM behaviour in an asymmetric Er(III) Schiff base complex: a combined experimental and theoretical study.

PubMed

Das, Chinmoy; Upadhyay, Apoorva; Vaidya, Shefali; Singh, Saurabh Kumar; Rajaraman, Gopalan; Shanmugam, Maheswaran

2015-04-11

An asymmetric erbium(III) Schiff base complex [Er(HL)2(NO3)3] was synthesized which shows SMM behaviour with an Ueff of 5.2 K. Dipolar interaction in 1 significantly reduced upon dilution which increases the barrier height to 51.5 K. Ab initio calculations were performed to shed light on the mechanism of magnetization relaxation.

Unexpected Catalytic Reactions of Silyl-protected Enoldiazoacetates With Nitrile Oxides That Form 5- Arylaminofuran-2(3H)-one-4-carboxylates

PubMed Central

Xu, Xinfang; Shabashov, Dmitry; Zavalij, Peter Y.; Doyle, Michael P.

2012-01-01

Silyl-protected enoldiazoacetates undergo dirhodium(II) catalyzed reactions with nitrile oxides to form acid-labile ketenimines via dipolar cycloaddition of nitrile oxides to a donor/acceptor cyclopropene and Lossen rearrangement of the dipolar adduct; acid catalysis converts the ketenimine to the furan product. PMID:22272728

High electronegativity multi-dipolar electron cyclotron resonance plasma source for etching by negative ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stamate, E.; Draghici, M.

2012-04-15

A large area plasma source based on 12 multi-dipolar ECR plasma cells arranged in a 3 x 4 matrix configuration was built and optimized for silicon etching by negative ions. The density ratio of negative ions to electrons has exceeded 300 in Ar/SF{sub 6} gas mixture when a magnetic filter was used to reduce the electron temperature to about 1.2 eV. Mass spectrometry and electrostatic probe were used for plasma diagnostics. The new source is free of density jumps and instabilities and shows a very good stability for plasma potential, and the dominant negative ion species is F{sup -}. Themore » magnetic field in plasma volume is negligible and there is no contamination by filaments. The etching rate by negative ions measured in Ar/SF{sub 6}/O{sub 2} mixtures was almost similar with that by positive ions reaching 700 nm/min.« less

Preparation, Characterization and Application of Optical Switch Probes.

PubMed

Petchprayoon, Chutima; Marriott, Gerard

2010-08-01

Optical switches represent a new class of molecular probe with applications in high contrast imaging and optical manipulation of protein interactions. Small molecule, organic optical switches based on nitrospirobenzopyran (NitroBIPS) and their reactive derivatives and conjugates undergo efficient, rapid and reversible, orthogonal optically-driven transitions between a colorless spiro (SP) state and a colored merocyanine (MC) state. The excited MC-state also emits fluorescence, which serves as readout of the state of the switch. Defined optical perturbations of SP and MC generate a defined waveform of MC-fluorescence that can be isolated against unmodulated background signals by using a digital optical lock-in detection approach or to control specific dipolar interactions on proteins. The protocols describe general procedures for the synthesis and spectroscopic characterization of NitroBIPS and specifically labeled conjugates along with methods for the manipulation of dipolar interactions on proteins and imaging of the MC-state of NitroBIPS within living cells.

Nuclear magnetic relaxation induced by exchange-mediated orientational randomization: longitudinal relaxation dispersion for a dipole-coupled spin-1/2 pair.

PubMed

Chang, Zhiwei; Halle, Bertil

2013-10-14

In complex biological or colloidal samples, magnetic relaxation dispersion (MRD) experiments using the field-cycling technique can characterize molecular motions on time scales ranging from nanoseconds to microseconds, provided that a rigorous theory of nuclear spin relaxation is available. In gels, cross-linked proteins, and biological tissues, where an immobilized macromolecular component coexists with a mobile solvent phase, nuclear spins residing in solvent (or cosolvent) species relax predominantly via exchange-mediated orientational randomization (EMOR) of anisotropic nuclear (electric quadrupole or magnetic dipole) couplings. The physical or chemical exchange processes that dominate the MRD typically occur on a time scale of microseconds or longer, where the conventional perturbation theory of spin relaxation breaks down. There is thus a need for a more general relaxation theory. Such a theory, based on the stochastic Liouville equation (SLE) for the EMOR mechanism, is available for a single quadrupolar spin I = 1. Here, we present the corresponding theory for a dipole-coupled spin-1/2 pair. To our knowledge, this is the first treatment of dipolar MRD outside the motional-narrowing regime. Based on an analytical solution of the spatial part of the SLE, we show how the integral longitudinal relaxation rate can be computed efficiently. Both like and unlike spins, with selective or non-selective excitation, are treated. For the experimentally important dilute regime, where only a small fraction of the spin pairs are immobilized, we obtain simple analytical expressions for the auto-relaxation and cross-relaxation rates which generalize the well-known Solomon equations. These generalized results will be useful in biophysical studies, e.g., of intermittent protein dynamics. In addition, they represent a first step towards a rigorous theory of water (1)H relaxation in biological tissues, which is a prerequisite for unravelling the molecular basis of soft-tissue contrast in clinical magnetic resonance imaging.

Transient effects in π-pulse sequences in MAS solid-state NMR

NASA Astrophysics Data System (ADS)

Hellwagner, Johannes; Wili, Nino; Ibáñez, Luis Fábregas; Wittmann, Johannes J.; Meier, Beat H.; Ernst, Matthias

2018-02-01

Dipolar recoupling techniques that use isolated rotor-synchronized π pulses are commonly used in solid-state NMR spectroscopy to gain insight into the structure of biological molecules. These sequences excel through their simplicity, stability towards radio-frequency (rf) inhomogeneity, and low rf requirements. For a theoretical understanding of such sequences, we present a Floquet treatment based on an interaction-frame transformation including the chemical-shift offset dependence. This approach is applied to the homonuclear dipolar-recoupling sequence Radio-Frequency Driven Recoupling (RFDR) and the heteronuclear recoupling sequence Rotational Echo Double Resonance (REDOR). Based on the Floquet approach, we show the influence of effective fields caused by pulse transients and discuss the advantages of pulse-transient compensation. We demonstrate experimentally that the transfer efficiency for homonuclear recoupling can be doubled in some cases in model compounds as well as in simple peptides if pulse-transient compensation is applied to the π pulses. Additionally, we discuss the influence of various phase cycles on the recoupling efficiency in order to reduce the magnitude of effective fields. Based on the findings from RFDR, we are able to explain why the REDOR sequence does not suffer in the recoupling efficiency despite the presence of effective fields.

Scrutinizing Molecular Mechanics Force Fields on the Submicrosecond Timescale with NMR Data

PubMed Central

Lange, Oliver F.; van der Spoel, David; de Groot, Bert L.

2010-01-01

Abstract Protein dynamics on the atomic level and on the microsecond timescale has recently become accessible from both computation and experiment. To validate molecular dynamics (MD) at the submicrosecond timescale against experiment we present microsecond MD simulations in 10 different force-field configurations for two globular proteins, ubiquitin and the gb3 domain of protein G, for which extensive NMR data is available. We find that the reproduction of the measured NMR data strongly depends on the chosen force field and electrostatics treatment. Generally, particle-mesh Ewald outperforms cut-off and reaction-field approaches. A comparison to measured J-couplings across hydrogen bonds suggests that there is room for improvement in the force-field description of hydrogen bonds in most modern force fields. Our results show that with current force fields, simulations beyond hundreds of nanoseconds run an increased risk of undergoing transitions to nonnative conformational states or will persist within states of high free energy for too long, thus skewing the obtained population frequencies. Only for the AMBER99sb force field have such transitions not been observed. Thus, our results have significance for the interpretation of data obtained with long MD simulations, for the selection of force fields for MD studies and for force-field development. We hope that this comprehensive benchmark based on NMR data applied to many popular MD force fields will serve as a useful resource to the MD community. Finally, we find that for gb3, the force-field AMBER99sb reaches comparable accuracy in back-calculated residual dipolar couplings and J-couplings across hydrogen bonds to ensembles obtained by refinement against NMR data. PMID:20643085

Determination of size and sign of hetero-nuclear coupling constants from 2D 19F-13C correlation spectra.

PubMed

Ampt, Kirsten A M; Aspers, Ruud L E G; Dvortsak, Peter; van der Werf, Ramon M; Wijmenga, Sybren S; Jaeger, Martin

2012-02-01

Fluorinated organic compounds have become increasingly important within the polymer and the pharmaceutical industry as well as for clinical applications. For the structural elucidation of such compounds, NMR experiments with fluorine detection are of great value due to the favorable NMR properties of the fluorine nucleus. For the investigation of three fluorinated compounds, triple resonance 2D HSQC and HMBC experiments were adopted to fluorine detection with carbon and/or proton decoupling to yield F-C, F-C{H}, F-C{C(acq)} and F-C{H,C(acq)} variants. Analysis of E.COSY type cross-peak patterns in the F-C correlation spectra led, apart from the chemical shift assignments, to determination of size and signs of the J(CH), J(CF), and J(HF) coupling constants. In addition, the fully coupled F-C HMQC spectrum of steroid 1 was interpreted in terms of E.COSY type patterns. This example shows how coupling constants due to different nuclei can be determined together with their relative signs from a single spectrum. The analysis of cross-peak patterns, as presented here, not only provides relatively straightforward routes to the determination of size and sign of hetero-nuclear J-couplings in fluorinated compounds, it also provides new and easy ways for the determination of residual dipolar couplings and thus for structure elucidation. The examples and results presented in this study may contribute to a better interpretation and understanding of various F-C correlation experiments and thereby stimulate their utilization. Copyright © 2011 Elsevier Inc. All rights reserved.

Methyl fluoride-13C in nematic liquid crystals: Anisotropy of the indirect 13C-19F spin-spin coupling and of the 1H, 13C, and 19F chemical shieldings

NASA Astrophysics Data System (ADS)

Jokisaari, J.; Hiltunen, Y.; Lounila, J.

1986-09-01

The anisotropy of the indirect 13C-19F spin-spin coupling tensor of methyl fluoride-13C in the liquid crystals ZLI 1167, EBBA, their mixtures, phase IV, and phase 1221 was studied by applying 1H and 19F NMR spectroscopy. The relative anisotropy ΔJCF/JCF gets values between -4.3 (in ZLI 1167) and +30.7 (in EBBA) when determined in the conventional way from the experimental dipolar coupling constants taking into account only harmonic vibrational corrections. The inclusion of the deformational corrections in both the direct and indirect C-F coupling tensors leads to a constant, solvent independent relative anisotropy of -2.5±0.2. This result is also obtained when a mixture of the liquid crystals ZLI 1167 and EBBA is used which mixture gives an undistorted geometry for methyl fluoride. The chemical shielding anisotropies ΔσH, ΔσC, and ΔσF for methyl fluoride were determined by applying the method of mixing two thermotropic nematogens (ZLI 1167 and EBBA) with opposite anisotropies of diamagnetic susceptibility. The results ΔσH =+5.2±0.2 ppm, ΔσC =+87±4 ppm, and ΔσF =-90±4 ppm are in fair agreement with theoretical calculations.

Unexpected catalytic reactions of silyl-protected enol diazoacetates with nitrile oxides that form 5-arylaminofuran-2(3H)-one-4-carboxylates.

PubMed

Xu, Xinfang; Shabashov, Dmitry; Zavalij, Peter Y; Doyle, Michael P

2012-02-03

Silyl-protected enol diazoacetates undergo dirhodium(II)-catalyzed reactions with nitrile oxides to form acid-labile ketenimines via dipolar cycloaddition of nitrile oxides to a donor/acceptor cyclopropene and Lossen rearrangement of the dipolar adduct; acid catalysis converts the ketenimine to the furan product. © 2012 American Chemical Society

Tuning dipolar magnetic interactions by controlling individual silica coating of iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Rivas Rojas, P. C.; Tancredi, P.; Moscoso Londoño, O.; Knobel, M.; Socolovsky, L. M.

2018-04-01

Single and fixed size core, core-shell nanoparticles of iron oxides coated with a silica layer of tunable thickness were prepared by chemical routes, aiming to generate a frame of study of magnetic nanoparticles with controlled dipolar interactions. The batch of iron oxides nanoparticles of 4.5 nm radii, were employed as cores for all the coated samples. The latter was obtained via thermal decomposition of organic precursors, resulting on nanoparticles covered with an organic layer that was subsequently used to promote the ligand exchange in the inverse microemulsion process, employed to coat each nanoparticle with silica. The amount of precursor and times of reaction was varied to obtain different silica shell thicknesses, ranging from 0.5 nm to 19 nm. The formation of the desired structures was corroborated by TEM and SAXS measurements, the core single-phase spinel structure was confirmed by XRD, and superparamagnetic features with gradual change related to dipolar interaction effects were obtained by the study of the applied field and temperature dependence of the magnetization. To illustrate that dipolar interactions are consistently controlled, the main magnetic properties are presented and analyzed as a function of center to center minimum distance between the magnetic cores.

Recoupling of Heteronuclear Dipolar Interactions with Rotational-Echo Double-Resonance at High Magic-Angle Spinning Frequencies

NASA Astrophysics Data System (ADS)

Jaroniec, Christopher P.; Tounge, Brett A.; Rienstra, Chad M.; Herzfeld, Judith; Griffin, Robert G.

2000-09-01

Heteronuclear dipolar recoupling with rotational-echo double-resonance (REDOR) is investigated in the rapid magic-angle spinning regime, where radiofrequency irradiation occupies a significant fraction of the rotor period (10-60%). We demonstrate, in two model 13C-15N spin systems, [1-13C, 15N] and [2-13C, 15N]glycine, that REDOR ΔS/S0 curves acquired at high MAS rates and relatively low recoupling fields are nearly identical to the ΔS/S0 curve expected for REDOR with ideal δ-function pulses. The only noticeable effect of the finite π pulse length on the recoupling is a minor scaling of the dipolar oscillation frequency. Experimental results are explained using both numerical calculations and average Hamiltonian theory, which is used to derive analytical expressions for evolution under REDOR recoupling sequences with different π pulse phasing schemes. For xy-4 and extensions thereof, finite pulses scale only the dipolar oscillation frequency by a well-defined factor. For other phasing schemes (e.g., xx-4 and xx¯-4) both the frequency and amplitude of the oscillation are expected to change.

Determination of the chirality of the saturated pyrrole in sulfmyoglobin using the nuclear Overhauser effect.

PubMed

Parker, W O; Chatfield, M J; La Mar, G N

1989-02-21

The interproton nuclear Overhauser effect (NOE) and paramagnetic dipolar relaxation rates for hyperfine-shifted resonances in the proton NMR spectra of sperm whale met-cyano sulfmyoglobin have led to the location and assignment of the proton signals of the heme pocket residue isoleucine 99 (FG5) in two sulfmyoglobin isomers. Dipolar relaxation rates of these protein signals indicate a highly conserved geometry of the heme pocket upon sulfmyoglobin formation, while the similar upfield direction of dipolar shifts for this residue to that observed in native sperm whale myoglobin reflects largely retained magnetic properties. Dipolar connectivity of this protein residue to the substituents of the reacted heme pyrrole ring B defines the stereochemistry of the puckered thiolene ring found in one isomer, with the 3-CH3 tilted out of the heme plane proximally. The chirality of the saturated carbons of pyrrole ring B in both the initial sulfmyoglobin product and the terminal alkaline product is consistent with a mechanism of formation in which an atom of sulfur is incorporated distally to form an episulfide across ring B, followed by reaction of the vinyl group to yield the thiolene ring that retains the C3 chirality.

Freezing point and solid-liquid interfacial free energy of Stockmayer dipolar fluids: a molecular dynamics simulation study.

PubMed

Wang, Jun; Apte, Pankaj A; Morris, James R; Zeng, Xiao Cheng

2013-09-21

Stockmayer fluids are a prototype model system for dipolar fluids. We have computed the freezing temperatures of Stockmayer fluids at zero pressure using three different molecular-dynamics simulation methods, namely, the superheating-undercooling method, the constant-pressure and constant-temperature two-phase coexistence method, and the constant-pressure and constant-enthalpy two-phase coexistence method. The best estimate of the freezing temperature (in reduced unit) for the Stockmayer (SM) fluid with the dimensionless dipole moment μ*=1, √2, √3 is 0.656 ± 0.001, 0.726 ± 0.002, and 0.835 ± 0.005, respectively. The freezing temperature increases with the dipolar strength. Moreover, for the first time, the solid-liquid interfacial free energies γ of the fcc (111), (110), and (100) interfaces are computed using two independent methods, namely, the cleaving-wall method and the interfacial fluctuation method. Both methods predict that the interfacial free energy increases with the dipole moment. Although the interfacial fluctuation method suggests a weaker interfacial anisotropy, particularly for strongly dipolar SM fluids, both methods predicted the same trend of interfacial anisotropy, i.e., γ100 > γ110 > γ111.

A novel dipolar dephasing method for the slow magic angle turning experiment.

PubMed

Hu, J Z; Taylor, C M; Pugmire, R J; Grant, D M

2001-09-01

Complete suppression of the resonances from protonated carbons in a slow magic angle spinning experiment can be achieved using five dipolar dephasing (Five-DD) periods distributed in one rotor period. This produces a spectrum containing only the spinning sidebands (SSB) from the nonprotonated carbons. It is shown that the SSB patterns corresponding to the nonprotonated carbons are not distorted over a wide range of dipolar dephasing times. Hence, this method can be used to obtain reliable principal values of the chemical shift tensors for each nonprotonated carbon. The Five-DD method can be readily incorporated into isotropic-anisotropic 2D experiments such as FIREMAT and 2D-PASS to facilitate the measurement of the (13)C chemical shift tensors in complex systems. Copyright 2001 Academic Press.

Cascade oxime formation, cyclization to a nitrone, and intermolecular dipolar cycloaddition.

PubMed

Furnival, Rachel C; Saruengkhanphasit, Rungroj; Holberry, Heather E; Shewring, Jonathan R; Guerrand, Hélène D S; Adams, Harry; Coldham, Iain

2016-11-22

Simple haloaldehydes, including enolisable aldehydes, were found to be suitable for the formation of cyclic products by cascade (domino) condensation, cyclisation, dipolar cycloaddition chemistry. This multi-component reaction approach to heterocyclic compounds was explored by using hydroxylamine, a selection of aldehydes, and a selection of activated dipolarophiles. Initial condensation gives intermediate oximes that undergo cyclisation with displacement of halide to give intermediate nitrones; these nitrones undergo in situ intermolecular dipolar cycloaddition reactions to give isoxazolidines. The cycloadducts from using dimethyl fumarate were treated with zinc/acetic acid to give lactam products and this provides an easy way to prepare pyrrolizinones, indolizinones, and pyrrolo[2,1-a]isoquinolinones. The chemistry is illustrated with a very short synthesis of the pyrrolizidine alkaloid macronecine and a formal synthesis of petasinecine.

Geometric stability spectra of dipolar Bose gases in tunable optical lattices

NASA Astrophysics Data System (ADS)

Corson, John P.; Wilson, Ryan M.; Bohn, John L.

2013-07-01

We examine the stability of quasi-two-dimensional dipolar Bose-Einstein condensates in the presence of weak optical lattices of various geometries. We find that when the condensate possesses a roton-maxon quasiparticle dispersion, the conditions for stability exhibit a strong dependence both on the lattice geometry and the polarization tilt. This results in rich structures in the system's stability diagram akin to spectroscopic signatures. We show how these structures originate from the mode matching of rotons to the perturbing lattice. In the case of a one-dimensional lattice, some of the features emerge only when the polarization axis is tilted into the plane of the condensate. Our results suggest that the stability diagram may be used as a novel means to spectroscopically measure rotons in dipolar condensates.

Development and application of high-resolution solid- state NMR dipolar recovery techniques for spin-1/2 nuclei

NASA Astrophysics Data System (ADS)

Joers, James M.

The use of magic angle spinning to obtain high resolution solid state spectra has been well documented. This resolution occurs by coherently averaging the chemical shift anisotropy and dipolar interactions to zero over the period of a full rotation. While this allows for higher resolution, the structural information is seemingly lost to the spectrometer eye. Thus, high resolution spectra and structural information appear to be mutually exlusive. Recently, the push in solid state NMR is the development of recoupling techniques which afford both high resolution and structural information. The following dissertation demonstrates the feasibility of implementing such experiments in solving real world problems, and is centered on devising a method to recover homonuclear dipolar interactions in the high resolution regime.

Solar Wind Plasma Interaction with Asteroid 16 Psyche: Implication for Formation Theories

NASA Astrophysics Data System (ADS)

Fatemi, Shahab; Poppe, Andrew R.

2018-01-01

The asteroid 16 Psyche is a primitive metal-rich asteroid that has not yet been visited by spacecraft. Based on remote observations, Psyche is most likely composed of iron and nickel metal; however, the history of its formation and solidification is still unknown. If Psyche is a remnant core of a differentiated planetesimal exposed by collisions, it opens a unique window toward understanding the cores of the terrestrial bodies, including the Earth and Mercury. If not, it is perhaps a reaccreted rubble pile that has never melted. In the former case, Psyche may have a remanent, dipolar magnetic field; in the latter case, Psyche may have no intrinsic field, but nevertheless would be a conductive object in the solar wind. We use Advanced Modeling Infrastructure in Space Simulation (AMITIS), a three-dimensional GPU-based hybrid model of plasma that self-consistently couples the interior electromagnetic response of Psyche (i.e., magnetic diffusion) to its ambient plasma environment in order to quantify the different interactions under these two cases. The model results provide estimates for the electromagnetic environment of Psyche, showing that the magnetized case and the conductive case present very different signatures in the solar wind. These results have implications for an accurate interpretation of magnetic field observations by NASA's Discovery mission (Psyche mission) to the asteroid 16 Psyche.

C-1311 (Symadex), a potential anti-cancer drug, intercalates into DNA between A and G moieties. NMR-derived and MD-refined stereostructure of the d(GAGGCCTC)2:C-1311 complex

NASA Astrophysics Data System (ADS)

Laskowski, Tomasz; Borzyszkowska, Julia; Grynda, Jakub; Mazerski, Jan

2017-08-01

Imidazoacridinone C-1311 (Symadex®) is an antitumor agent which has been recommended for Phase II clinical trials a few years ago. Previously, it was shown experimentally that during the initial stage of its action C-1311 forms stable intercalation complexes with DNA duplexes. Herein, a NMR-derived stereostructure of d(GAGGCCTC)2:C-1311 complex was reported. The ligand was found locating itself between A and G moieties, forming symmetrical DNA:drug 1:2 mol/mol complex. Intercalation site was located upon the DNA-ligand proton/proton dipolar couplings observed in the NOESY spectrum and the performed MD simulations. NMR-derived stereostructure was hence refined by restrained MD using distance restraints obtained from the NOESY data and the result was compared with MD-derived structure of the proposed complex, obtained from the calculations performed with distance restraints applied only for hydrogen bonds in the terminal GC base pairs. The results of both simulations were coherent. Basing on the observed C-1311's intercalation sites and on our previous results concerning the d(CGATCG)2:C-1311 complex, we stated that AG/GA sequences are the preferred binding sites of imidazoacridinone C-1311.

Beyond dipolar regime in high-order plasmon mode bowtie antennas

NASA Astrophysics Data System (ADS)

Cuche, Aurélien; Viarbitskaya, Sviatlana; Kumar, Upkar; Sharma, Jadab; Arbouet, Arnaud; Girard, Christian; Dujardin, Erik

2017-03-01

Optical nanoantennas have shown their great potential for far-field to near-field coupling and for light confinement in subwavelength volumes. Here, we report on a multimodal configuration for bright and polarization-dependent bowtie antenna based on large and highly crystalline gold prisms. Each individual prism constituting an antenna arm sustains high order plasmon modes in the visible and near infrared range that allow for high field confinement and two-dimensional optical information propagation. We demonstrate by scanning two-photon luminescence (TPL) microscopy and numerical simulations based on the Green dyadic method that these bowtie antennas result in intense hot spots in different antenna locations as a function of the incident polarization. Finally, we quantify the local field enhancement above the antennas by computing the normalized total decay rate of a molecular system placed in the near field of the antenna gap as a function of the dipole orientation. We demonstrate the existence of a subtle relation between antenna geometry, polarization dependence and field enhancement. These new multimodal optical antennas are excellent far field to near field converter and they open the door for new strategies in the design of coplanar optical components for a wide range of applications including sensing, energy conversion or integrated information processing.

Imaging Magnetic Vortices Dynamics Using Lorentz Electron Microscopy with GHz Excitations

NASA Astrophysics Data System (ADS)

Zhu, Yimei

2015-03-01

Magnetic vortices in thin films are naturally formed spiral spin configurations with a core polarization pointing out of the film plane. They typically represent ground states with high structural and thermal stability as well as four different chirality-polarity combinations, offering great promise in the development of spin-based devices. For applications to spin oscillators, non-volatile memory and logic devices, the fundamental understanding and precise control of vortex excitations and dynamic switching behavior are essential. The compact dimensionality and fast spin dynamics set grand challenges for direct imaging technologies. Recently, we have developed a unique method to directly visualize the dynamic magnetic vortex motion using advanced Lorentz electron microscopy combined with GHz electronic excitations. It enables us to map the orbit of a magnetic vortex core in a permalloy square with <5nm resolution and to reveal subtle changes of the gyrotropic motion as the vortex is driven through resonance. Further, in multilayer spin-valve disks, we probed the strongly coupled coaxial vortex motion in the dipolar- and indirect exchange-coupled regimes and unraveled the underlying coherence and modality. Our approach is complementary to X-ray magnetic circular dichroism and is of general interest to the magnetism community as it paves a way to study fundamental spin phenomena with unprecedented resolution and accuracy. Collaborations with S.D. Pollard, J.F. Pulecio, D.A. Arena and K.S. Buchanan are acknowledged. Work supported by DOE-BES, Material Sciences and Engineering Division, under Contract No. DE-AC02-98CH10886.

Quantifying entanglement of rotor chains using basis truncation: Application to dipolar endofullerene peapods.

PubMed

Halverson, Tom; Iouchtchenko, Dmitri; Roy, Pierre-Nicholas

2018-02-21

We propose a variational approach for the calculation of the quantum entanglement entropy of assemblies of rotating dipolar molecules. A basis truncation scheme based on the total angular momentum quantum number is proposed. The method is tested on hydrogen fluoride (HF) molecules confined in C 60 fullerene cages themselves trapped in a nanotube to form a carbon peapod. The rotational degrees of freedom of the HF molecules and dipolar interactions between neighboring molecules are considered in our model Hamiltonian. Both screened and unscreened dipoles are simulated and results are obtained for the ground state and one excited state that is expected to be accessible via a far-infrared collective excitation. The effect of basis truncation on energetic and entanglement properties is examined and discussed in terms of size extensivity. It is empirically found that for unscreened dipoles, a total angular momentum cutoff that increases linearly with the number of rotors is required in order to obtain proper system size scaling of the chemical potential and entanglement entropy. Recent experiments [A. Krachmalnicoff et al., Nat. Chem. 8, 953 (2016)] suggest substantial screening of the HF dipole moment, so much smaller basis sets are required to obtain converged results in this realistic case. Static correlation functions are also computed and are shown to decay much quicker in the case of screened dipoles. Our variational results are also used to test the accuracy of perturbative and pairwise ansatz treatments.

Energy conversion and dissipation at dipolarization fronts: Theory, modeling and MMS observations

NASA Astrophysics Data System (ADS)

Sitnov, M. I.; Motoba, T.; Merkin, V. G.; Ohtani, S.; Cohen, I. J.; Mauk, B.; Vines, S. K.; Anderson, B. J.; Moore, T. E.; Torbert, R. B.; Giles, B. L.; Burch, J. L.

2017-12-01

Magnetic reconnection is one of the most important energy conversion mechanisms in space plasmas. In the classical picture it converts the energy of antiparallel magnetic fields into the kinetic and thermal energy of accelerated plasma particles in reconnection exhausts. It also involves energy dissipation near the X-line. This classical picture may be substantially modified in real space plasma configurations, such as the dayside magnetopause and the magnetotail. In particular, in the magnetotail the flows of accelerated particles may be strongly asymmetric along the tail with the domination of earthward flows. At the same time, strong energy conversion and even dissipation may occur away from the X-line, in particular, at dipolarization fronts. Here we present a theoretical picture of spontaneous magnetotail reconnection based on 3-D PIC simulations with the focus on plasma bulk flows, energy conversion and dissipation. This picture is compared with some observations from the MMS tail season. An important finding from these observations is that dipolarizations fronts may not only be regions of the total energy conversion with jE>0, but they may also be the sites of energy dissipation, both positive (jE'>0, E' is the electric field E in the system moving with one of the plasma species) and negative (jE'<0). Observations are further compared with theory and modeling that predict the specific location and sign of the energy dissipation at fronts depending on their evolution phase (e.g., formation, propagation, braking).

Ferroelectric self-assembled molecular materials showing both rectifying and switchable conductivity

PubMed Central

Gorbunov, Andrey V.; Garcia Iglesias, Miguel; Guilleme, Julia; Cornelissen, Tim D.; Roelofs, W. S. Christian; Torres, Tomas; González-Rodríguez, David; Meijer, E. W.; Kemerink, Martijn

2017-01-01

Advanced molecular materials that combine two or more physical properties are typically constructed by combining different molecules, each being responsible for one of the properties required. Ideally, single molecules could take care of this combined functionality, provided they are self-assembled correctly and endowed with different functional subunits whose strong electronic coupling may lead to the emergence of unprecedented and exciting properties. We present a class of disc-like semiconducting organic molecules that are functionalized with strong dipolar side groups. Supramolecular organization of these materials provides long-range polar order that supports collective ferroelectric behavior of the side groups as well as charge transport through the stacked semiconducting cores. The ferroelectric polarization in these supramolecular polymers is found to couple to the charge transport and leads to a bulk conductivity that is both switchable and rectifying. An intuitive model is developed and found to quantitatively reproduce the experimental observations. In a larger perspective, these results highlight the possibility of modulating material properties using the large electric fields associated with ferroelectric polarization. PMID:28975150

Determination of NH proton chemical shift anisotropy with 14N-1H heteronuclear decoupling using ultrafast magic angle spinning solid-state NMR

NASA Astrophysics Data System (ADS)

Pandey, Manoj Kumar; Nishiyama, Yusuke

2015-12-01

The extraction of chemical shift anisotropy (CSA) tensors of protons either directly bonded to 14N nuclei (I = 1) or lying in their vicinity using rotor-synchronous recoupling pulse sequence is always fraught with difficulty due to simultaneous recoupling of 14N-1H heteronuclear dipolar couplings and the lack of methods to efficiently decouple these interactions. This difficulty mainly arises from the presence of large 14N quadrupolar interactions in comparison to the rf field that can practically be achieved. In the present work it is demonstrated that the application of on-resonance 14N-1H decoupling with rf field strength ∼30 times weaker than the 14N quadrupolar coupling during 1H CSA recoupling under ultrafast MAS (90 kHz) results in CSA lineshapes that are free from any distortions from recoupled 14N-1H interactions. With the use of extensive numerical simulations we have shown the applicability of our proposed method on a naturally abundant L-Histidine HCl·H2O sample.

Order in dense hydrogen at low temperatures

PubMed Central

Edwards, B.; Ashcroft, N. W.

2004-01-01

By increase in density, impelled by pressure, the electronic energy bands in dense hydrogen attain significant widths. Nevertheless, arguments can be advanced suggesting that a physically consistent description of the general consequences of this electronic structure can still be constructed from interacting but state-dependent multipoles. These reflect, in fact self-consistently, a disorder-induced localization of electron states partially manifesting the effects of proton dynamics; they retain very considerable spatial inhomogeneity (as they certainly do in the molecular limit). This description, which is valid provided that an overall energy gap has not closed, leads at a mean-field level to the expected quadrupolar coupling, but also for certain structures to the eventual emergence of dipolar terms and their coupling when a state of broken charge symmetry is developed. A simple Hamiltonian incorporating these basic features then leads to a high-density, low-temperature phase diagram that appears to be in substantial agreement with experiment. In particular, it accounts for the fact that whereas the phase I–II phase boundary has a significant isotope dependence, the phase II–III boundary has very little. PMID:15028839

Optical interactions in a plasmonic particle coupled to a metallic film

NASA Astrophysics Data System (ADS)

Lévêque, Gäetan; Martin, Olivier J. F.

2006-10-01

The interplay between localized surface plasmon (LSP) and surface plasmon-polariton (SPP) is studied in detail in a system composed of a three-dimensional gold particle located at a short distance from a gold thin film. Important frequency shifts of the LSP associated with the particle are observed for spacing distances between 0 and 50 nm. Beyond this distance the LSP and SPP resonances overlap, although some cavity effects between the particle and the film can still be observed. In particular, when the spacing increases the field in the cavity decreases more slowly than one would expect from a simple image dipole interpretation. For short separations the coupling between the particle and the film can produce a dramatic enhancement of the electromagnetic field in the space between them, where the electric field intensity can reach 5000 times that of the illumination field. Several movies show the spectral and time evolutions of the field distribution in the system both in and out of resonance. The character of the different modes excited in the system is studied. They include dipolar and quadrupolar modes, the latter exhibiting essentially a magnetic response.

ADRF experiments using near n.pi pulse strings. [Adiabatic Demagnetization due to Radio Frequency pulses

NASA Technical Reports Server (NTRS)

Rhim, W. K.; Burum, D. P.; Elleman, D. D.

1977-01-01

Adiabatic demagnetization (ADRF) can be achieved in a dipolar coupled nuclear spin system in solids by applying a string of short RF pulses and gradually modulating the pulse amplitudes or pulse angles. This letter reports an adiabatic inverse polarization effect in solids and a rotary spin echo phenomenon observed in liquids when the pulse angle is gradually changed across integral multiples of pi during a string of RF pulses. The RF pulse sequence used is illustrated along with the NMR signal from a CaF2 single crystal as observed between the RF pulses and the rotary spin echo signal observed in liquid C6F6 for n = 2. The observed effects are explained qualitatively on the basis of average Hamiltonian theory.

Ultrafast laser control of autoionizing resonances observed in attosecond transient absorption

NASA Astrophysics Data System (ADS)

Liao, Chen-Ting; Harkema, Nathan; Sandhu, Arvinder

2017-04-01

Attosecond and femtosecond extreme ultraviolet (XUV) pulses can be used to probe electron dynamics in high-lying excited states that autoionize on a femtosecond timescale, thus providing information on the process of Auger decay and its interference with the continua. Here we utilize XUV pulses in connection with infrared (IR) pulses to perform attosecond transient absorption spectroscopy of the impulsive response of argon autoionizing Rydberg states in the vicinity of the 3s-1 4 p resonance. We show that by tuning the time delay and field polarization of IR pulse, it is possible to control the dipolar coupling between neighboring states and hence the spectral line shape of the resonance, such as the transition between Breit-Wigner to Beutler-Fano profiles. NSF Grant No. PHY-1505556.

Measurement of residual chemical shift anisotropies in compressed polymethylmethacrylate gels. Automatic compensation of gel isotropic shift contribution.

PubMed

Hallwass, Fernando; Teles, Rubens R; Hellemann, Erich; Griesinger, Christian; Gil, Roberto R; Navarro-Vázquez, Armando

2018-05-01

Mechanical compression of polymer gels provides a simple way for the measurement of residual chemical shift anisotropies, which then can be employed, on its own, or in combination with residual dipolar couplings, for structural elucidation purposes. Residual chemical shift anisotropies measured using compression devices needed a posteriori correction to account for the increase of the polymer to solvent ratio inside the swollen gel. This correction has been cast before in terms of a single-free parameter which, as shown here, can be simultaneously optimized along with the components of the alignment tensor while still retaining discriminating power of the different relative configurations as illustrated in the stereochemical analysis of α-santonin and 10-epi-8-deoxycumambrin B. Copyright © 2018 John Wiley & Sons, Ltd.

Dynamic generation of light states with discrete symmetries

NASA Astrophysics Data System (ADS)

Cordero, S.; Nahmad-Achar, E.; Castaños, O.; López-Peña, R.

2018-01-01

A dynamic procedure is established within the generalized Tavis-Cummings model to generate light states with discrete point symmetries, given by the cyclic group Cn. We consider arbitrary dipolar coupling strengths of the atoms with a one-mode electromagnetic field in a cavity. The method uses mainly the matter-field entanglement properties of the system, which can be extended to any number of three-level atoms. An initial state constituted by the superposition of two states with definite total excitation numbers, |ψ〉 M1,and |ψ〉 M 2, is considered. It can be generated by the proper selection of the time of flight of an atom passing through the cavity. We demonstrate that the resulting Husimi function of the light is invariant under cyclic point transformations of order n =| M1-M2| .

The hyperfine structure in the rotational spectra of D{sub 2}{sup 17}O and HD{sup 17}O: Confirmation of the absolute nuclear magnetic shielding scale for oxygen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Puzzarini, Cristina, E-mail: cristina.puzzarini@unibo.it; Cazzoli, Gabriele; Harding, Michael E.

2015-03-28

Guided by theoretical predictions, the hyperfine structures of the rotational spectra of mono- and bideuterated-water containing {sup 17}O have been experimentally investigated. To reach sub-Doppler resolution, required to resolve the hyperfine structure due to deuterium quadrupole coupling as well as to spin-rotation (SR) and dipolar spin-spin couplings, the Lamb-dip technique has been employed. The experimental investigation and in particular, the spectral analysis have been supported by high-level quantum-chemical computations employing coupled-cluster techniques and, for the first time, a complete experimental determination of the hyperfine parameters involved was possible. The experimentally determined {sup 17}O spin-rotation constants of D{sub 2}{sup 17}O andmore » HD{sup 17}O were used to derive the paramagnetic part of the corresponding nuclear magnetic shielding constants. Together with the computed diamagnetic contributions as well as the vibrational and temperature corrections, the latter constants have been employed to confirm the oxygen nuclear magnetic shielding scale, recently established on the basis of spin-rotation data for H{sub 2}{sup 17}O [Puzzarini et al., J. Chem. Phys. 131, 234304 (2009)].« less

Novel NMR tools to study structure and dynamics of biomembranes.

PubMed

Gawrisch, Klaus; Eldho, Nadukkudy V; Polozov, Ivan V

2002-06-01

Nuclear magnetic resonance (NMR) studies on biomembranes have benefited greatly from introduction of magic angle spinning (MAS) NMR techniques. Improvements in MAS probe technology, combined with the higher magnetic field strength of modern instruments, enables almost liquid-like resolution of lipid resonances. The cross-relaxation rates measured by nuclear Overhauser enhancement spectroscopy (NOESY) provide new insights into conformation and dynamics of lipids with atomic-scale resolution. The data reflect the tremendous motional disorder in the lipid matrix. Transfer of magnetization by spin diffusion along the proton network of lipids is of secondary relevance, even at a long NOESY mixing time of 300 ms. MAS experiments with re-coupling of anisotropic interactions, like the 13C-(1)H dipolar couplings, benefit from the excellent resolution of 13C shifts that enables assignment of the couplings to specific carbon atoms. The traditional 2H NMR experiments on deuterated lipids have higher sensitivity when conducted on oriented samples at higher magnetic field strength. A very large number of NMR parameters from lipid bilayers is now accessible, providing information about conformation and dynamics for every lipid segment. The NMR methods have the sensitivity and resolution to study lipid-protein interaction, lateral lipid organization, and the location of solvents and drugs in the lipid matrix.

A modified abstraction of Sierpiński fractals towards enhanced sensitivity of a cross-coupled bow-tie nanostructure

NASA Astrophysics Data System (ADS)

Hasan, Dihan; Lee, Chengkuo

2018-06-01

We experimentally demonstrate a modified abstraction of a fractal geometry (up to order M = 2), namely the Sierpiński fractal, with intrinsic self-similarity for a multitude of infrared sensing applications. The modification particularly strengthens the dipolar resonance and enables optical magnetism at longer wavelengths on a relatively miniaturized footprint. In contrast to the conventional resonant sensing, we harness the broadband electric field enhancement of the modified fractal patterns originating from the lightning rod effect in the non-resonant regime. We demonstrate strong enhancement of molecular absorption at mid-IR by the fractal patterns in the non-resonant regime even under extreme thermal broadening. Finally, we extend the work towards the functional study of the molecular fingerprint of ultra-thin film (∼5 nm) on a non-complementary metamaterial platform in the non-resonant regime. With the help of the solid state chemical dewetting of the monolayer, we also successfully demonstrate a new type of cross-coupling mediated sensitivity of the multispectral and mutually coupled fractal patterns. The research clearly indicates the usefulness of broadband electric field enhancement by the second order fractal pattern for on chip, complete profiling of mid-IR fingerprints of biological elements, i.e. cell, and protein monolayer on a limited footprint and under versatile morphological states.

Lithium formate for EPR dosimetry: radiation-induced radical trapping at low temperatures.

PubMed

Krivokapić, André; Aalbergsjø, Siv G; De Cooman, Hendrik; Hole, Eli Olaug; Nelson, William H; Sagstuen, Einar

2014-05-01

Radiation-induced primary radicals in lithium formate. A material used in EPR dosimetry have been studied using electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR) and ENDOR-Induced EPR (EIE) techniques. In this study, single crystals were X irradiated at 6-8 K and radical formation at these and higher temperatures were investigated. Periodic density functional theory calculations were used to assist in assigning the radical structures. Mainly two radicals are present at 6 K, the well-known CO2(•-) radical and a protonated electron-gain product. Hyperfine coupling tensors for proton and lithium interactions were obtained for these two radicals and show that the latter radical exists in four conformations with various degrees of bending at the radical center. Pairs of CO2(•-) radicals were also observed and the tensor for the electron-electron dipolar coupling was determined for the strongest coupled pair, which exhibited the largest spectral intensity. Upon warming, both the radical pairs and the reduction product decay, the latter apparently by a transient species. Above 200 K the EPR spectrum was mainly due to the CO2(•-) (mono) radicals, which were previously characterized as the dominant species present at room temperature and which account for the dosimetric EPR signal.

Interpretation of magnetization transfer from inhomogeneously broadened lines (ihMT) in tissues as a dipolar order effect within motion restricted molecules

NASA Astrophysics Data System (ADS)

Varma, G.; Girard, O. M.; Prevost, V. H.; Grant, A. K.; Duhamel, G.; Alsop, D. C.

2015-11-01

Comparison of off-resonance saturation with single and dual frequency irradiation indicates a contribution of inhomogeneously broadened lines to magnetization transfer in tissues. This inhomogeneous magnetization transfer (ihMT) phenomenon can be exploited to produce images that highlight tissues containing myelin, in vivo. Here, a model for ihMT is described that includes dipolar order effects from magnetization associated with motion-restricted macromolecules. In this model, equal irradiation at positive and negative frequency offsets eliminates dipolar order and achieves greater saturation than irradiation at a single offset frequency using the same power. Fitting of mouse and human volunteer brain data at different irradiation powers and offset frequencies was performed to assess the relevance of the model and approximate tissue parameters. A key parameter in determining ihMT signal was found to be the relaxation time T1D associated with the dipolar order reservoir and the fraction f of the semi-solid, bound magnetization that possessed a nonzero T1D. Indeed, better fits of myelinated tissue were achieved when assuming f ≠ 1. From such fits, estimated T1Ds of mice in the white matter, (34 ± 14)ms, were much longer than in muscle, T1D = (1 ± 1)ms and the average f from white matter volunteer data was 2.2 times greater than that in grey matter. The combination of f and longer T1Ds was primarily responsible for the much higher ihMT in myelinated tissues, and provided explanation for the species variation. This dipolar order ihMT model should help guide future research, pulse sequence optimization, and clinical applications.

Variations of High-Energy Ions during Fast Plasma Flows and Dipolarization in the Plasma Sheet: Comparison Among Different Ion Species

NASA Astrophysics Data System (ADS)

Ohtani, S.; Nose, M.; Miyashita, Y.; Lui, A.

2014-12-01

We investigate the responses of different ion species (H+, He+, He++, and O+) to fast plasma flows and local dipolarization in the plasma sheet in terms of energy density. We use energetic (9-210 keV) ion composition measurements made by the Geotail satellite at r = 10~31 RE. The results are summarized as follows: (1) whereas the O+-to-H+ ratio decreases with earthward flow velocity, it increases with tailward flow velocity with Vx dependence steeper for perpendicular flows than for parallel flows; (2) for fast earthward flows, the energy density of each ion species increases without any clear preference for heavy ions; (3) for fast tailward flows the ion energy density increases initially, then it decreases to below pre-flow levels except for O+; (4) the O+-to-H+ ratio does not increase through local dipolarization irrespective of dipolarization amplitude, background BZ, X distance, and VX; (5) in general, the H+ and He++ ions behave similarly. Result (1) can be attributed to radial transport along with the earthward increase of the background O+-to-H+ ratio. Results (2) and (4) indicate that ion energization associated with local dipolarization is not mass-dependent possibly because in the energy range of our interest the ions are not magnetized irrespective of species. In the tailward outflow region of reconnection, where the plasma sheet becomes thinner, the H+ ions escape along the field line more easily than the O+ ions, which possibly explains result (3). Result (5) suggests that the solar wind is the primary source of the high-energy H+ ions.

Quantum phases of dipolar rotors on two-dimensional lattices

NASA Astrophysics Data System (ADS)

Abolins, B. P.; Zillich, R. E.; Whaley, K. B.

2018-03-01

The quantum phase transitions of dipoles confined to the vertices of two-dimensional lattices of square and triangular geometry is studied using path integral ground state quantum Monte Carlo. We analyze the phase diagram as a function of the strength of both the dipolar interaction and a transverse electric field. The study reveals the existence of a class of orientational phases of quantum dipolar rotors whose properties are determined by the ratios between the strength of the anisotropic dipole-dipole interaction, the strength of the applied transverse field, and the rotational constant. For the triangular lattice, the generic orientationally disordered phase found at zero and weak values of both dipolar interaction strength and applied field is found to show a transition to a phase characterized by net polarization in the lattice plane as the strength of the dipole-dipole interaction is increased, independent of the strength of the applied transverse field, in addition to the expected transition to a transverse polarized phase as the electric field strength increases. The square lattice is also found to exhibit a transition from a disordered phase to an ordered phase as the dipole-dipole interaction strength is increased, as well as the expected transition to a transverse polarized phase as the electric field strength increases. In contrast to the situation with a triangular lattice, on square lattices, the ordered phase at high dipole-dipole interaction strength possesses a striped ordering. The properties of these quantum dipolar rotor phases are dominated by the anisotropy of the interaction and provide useful models for developing quantum phases beyond the well-known paradigms of spin Hamiltonian models, implementing in particular a novel physical realization of a quantum rotor-like Hamiltonian that possesses an anisotropic long range interaction.

Corresponding-states behavior of a dipolar model fluid with variable dispersion interactions and its relevance to the anomalies of hydrogen fluoride

NASA Astrophysics Data System (ADS)

Weiss, Volker C.; Leroy, Frédéric

2016-06-01

More than two decades ago, the elusiveness of a liquid-vapor equilibrium and a corresponding critical point in simulations of the supposedly simple model of dipolar hard spheres came as a surprise to many liquid matter theorists. van Leeuwen and Smit [Phys. Rev. Lett. 71, 3991 (1993)] showed that a minimum of attractive dispersion interactions among the dipolar particles may be needed to observe regular fluid behavior. Here, we adopt their approach and use an only slightly modified model, in which the original point dipole is replaced by a dipole moment produced by charges that are separated in space, to study the influence of dispersion interactions of variable strength on the coexistence and interfacial properties of a polar fluid. The thermophysical properties are discussed in terms of Guggenheim's corresponding-states approach. In this way, the coexistence curve, the critical compressibility factor, the surface tension, Guggenheim's ratio, and modifications of Guldberg's and Trouton's rules (related to the vapor pressure and the enthalpy of vaporization) are analyzed. As the importance of dispersion is decreased, a crossover from simple-fluid behavior to that characteristic of strongly dipolar systems takes place; for some properties, this transition is monotonic, but for others it occurs non-monotonically. For strongly dipolar systems, the reduced surface tension is very low, whereas Guggenheim's ratio and Guldberg's ratio are found to be high. The critical compressibility factor is smaller, and the coexistence curve is wider and more skewed than for simple fluids. For very weak dispersion, liquid-vapor equilibrium is still observable, but the interfacial tension is extremely low and may, eventually, vanish marking the end of the existence of a liquid phase. We discuss the implications of our findings for real fluids, in particular, for hydrogen fluoride.

Van Allen Probes Observations of Magnetic Field Dipolarization and Its Associated O+ Flux Variations in the Inner Magnetosphere at L 6.6

NASA Technical Reports Server (NTRS)

Nose, M.; Keika, K.; Kletzing, C. A.; Spence, H. E.; Smith, C. W.; MacDowall, R. J.; Reeves, G. D.; Larsen, B. A.; Mitchell, D. G.

2016-01-01

We investigate the magnetic field dipolarization in the inner magnetosphere and its associated ion flux variations, using the magnetic field and energetic ion flux data acquired by the Van Allen Probes. From a study of 74 events that appeared at L= 4.5-6.6 between 1 October 2012 and 31 October 2013, we reveal the following characteristics of the dipolarization in the inner magnetosphere: (1) its time scale is approximately 5 min; (2) it is accompanied by strong magnetic fluctuations that have a dominant frequency close to the O+ gyrofrequency; (3) ion fluxes at 20-50 keV are simultaneously enhanced with larger magnitudes for O+ than for H+; (4) after a few minutes of the dipolarization, the flux enhancement at 0.1-5 keV appears with a clear energy-dispersion signature only for O+; and (5) the energy-dispersed O+ flux enhancement appears in directions parallel or antiparallel to the magnetic field. From these characteristics, we discuss possible mechanisms that can provide selective acceleration to O+ ions at > 20 keV. We conclude that O+ ions at L= 5.4-6.6 undergo nonadiabatic local acceleration caused by oscillating electric field associated with the magnetic fluctuations and/or adiabatic convective transport from the plasma sheet to the inner magnetosphere by the impulsive electric field. At L= 4.5-5.4, however, only the former acceleration is plausible. We also conclude that the field-aligned energy-dispersed O+ ions at 0.1-5 keV originate from the ionosphere and are extracted nearly simultaneously to the onset of the dipolarization.

Effect of magnetic dipolar interactions on temperature dependent magnetic hyperthermia in ferrofluids

NASA Astrophysics Data System (ADS)

Palihawadana-Arachchige, Maheshika; Nemala, Humeshkar; Naik, Vaman M.; Naik, Ratna

2017-01-01

Magnetic hyperthermia (MHT), where localized heating is generated when magnetic nanoparticles (MNPs) are subjected to a radiofrequency magnetic field, has a great potential as a non-invasive cancer therapy treatment. The efficiency of heat generation depends on the magnetic properties of MNPs, such as saturation magnetization (Ms) and magnetic anisotropy (K), as well as the particle size distribution and magnetic dipolar interactions. We have investigated MHT in two Fe3O4 ferrofluids prepared by co-precipitation (CP) and hydrothermal (HT) synthesis methods showing similar physical particle size distribution (14 ± 4 nm) and saturation magnetization (70 ± 2 emu/g of Fe3O4) but very different specific absorption rates (SAR) of ˜110 W/g and ˜40 W/g at room temperature (measured with an ac magnetic field amplitude of 240 Oe and a frequency of 375 kHz). This observed reduction in SAR has been explained by taking into account the dipolar interactions and the distribution of the magnetic core size of MNPs in ferrofluids. The HT ferrofluid shows a higher effective dipolar interaction and a wider distribution of the magnetic core size of MNPs compared to those of the CP ferrofluid. We have fitted the temperature dependent SAR data using the linear response theory, incorporating an effective dipolar interaction, to determine the magnetic anisotropy constant of MNPs prepared by CP (22 ± 2 kJ/m3) and HT (26 ± 2 kJ/m3) synthesis methods. These values are in good agreement with the magnetic anisotropy constant determined using frequency and temperature dependent magnetic susceptibility data obtained on powder samples.

Long-range dipolar order and dispersion forces in polar liquids

NASA Astrophysics Data System (ADS)

Besford, Quinn Alexander; Christofferson, Andrew Joseph; Liu, Maoyuan; Yarovsky, Irene

2017-11-01

Complex solvation phenomena, such as specific ion effects, occur in polar liquids. Interpretation of these effects in terms of structure and dispersion forces will lead to a greater understanding of solvation. Herein, using molecular dynamics, we probe the structure of polar liquids through specific dipolar pair correlation functions that contribute to the potential of mean force that is "felt" between thermally rotating dipole moments. It is shown that unique dipolar order exists at separations at least up to 20 Å for all liquids studied. When the structural order is compared with a dipolar dispersion force that arises from local co-operative enhancement of dipole moments, a strong agreement is found. Lifshitz theory of dispersion forces was compared with the structural order, where the theory is validated for all liquids that do not have significant local dipole correlations. For liquids that do have significant local dipole correlations, specifically liquid water, Lifshitz theory underestimates the dispersion force by a factor of 5-10, demonstrating that the force that leads to the increased structure in liquid water is missed by Lifshitz theory of van der Waals forces. We apply similar correlation functions to an ionic aqueous system, where long-range order between water's dipole moment and a single chloride ion is found to exist at 20 Å of separation, revealing a long-range perturbation of water's structure by an ion. Furthermore, we found that waters within the 1st, 2nd, and 3rd solvation shells of a chloride ion exhibit significantly enhanced dipolar interactions, particularly with waters at larger distances of separation. Our results provide a link between structures, dispersion forces, and specific ion effects, which may lead to a more robust understanding of solvation.

Nanoscale control of competing interactions and geometrical frustration in a dipolar trident lattice

DOE PAGES

Farhan, Alan; Petersen, Charlotte F.; Dhuey, Scott; ...

2017-10-17

Geometrical frustration occurs when entities in a system, subject to given lattice constraints, are hindered to simultaneously minimize their local interactions. In magnetism, systems incorporating geometrical frustration are fascinating, as their behavior is not only hard to predict, but also leads to the emergence of exotic states of matter. Here, we provide a first look into an artificial frustrated system, the dipolar trident lattice, where the balance of competing interactions between nearest-neighbor magnetic moments can be directly controlled, thus allowing versatile tuning of geometrical frustration and manipulation of ground state configurations. Our findings not only provide the basis for futuremore » studies on the low-temperature physics of the dipolar trident lattice, but also demonstrate how this frustration-by-design concept can deliver magnetically frustrated metamaterials.« less

Fingering instabilities and pattern formation in a two-component dipolar Bose-Einstein condensate

NASA Astrophysics Data System (ADS)

Xi, Kui-Tian; Byrnes, Tim; Saito, Hiroki

2018-02-01

We study fingering instabilities and pattern formation at the interface of an oppositely polarized two-component Bose-Einstein condensate with strong dipole-dipole interactions in three dimensions. It is shown that the rotational symmetry is spontaneously broken by fingering instability when the dipole-dipole interactions are strengthened. Frog-shaped and mushroom-shaped patterns emerge during the dynamics due to the dipolar interactions. We also demonstrate the spontaneous density modulation and domain growth of a two-component dipolar BEC in the dynamics. Bogoliubov analyses in the two-dimensional approximation are performed, and the characteristic lengths of the domains are estimated analytically. Patterns resembling those in magnetic classical fluids are modulated when the number ratio of atoms, the trap ratio of the external potential, or tilted polarization with respect to the z direction is varied.

Towards novel multiferroic and magnetoelectric materials: dipole stability in tetragonal tungsten bronzes

PubMed Central

Rotaru, Andrei; Miller, Andrew J.; Arnold, Donna C.; Morrison, Finlay D.

2014-01-01

We discuss the strategy for development of novel functional materials with the tetragonal tungsten bronze structure. From the starting composition Ba6GaNb9O30, the effect of A- and B-site substitutions on the dielectric properties is used to develop an understanding of the origin and stability of the dipolar response in these compounds. Both tetragonal strain induced by large B-site cations and local strain variations created by isovalent A-site substitutions enhance dipole stability but result in a dilute, weakly correlated dipolar response and canonical relaxor behaviour. Decreasing cation size at the perovskite A2-site increases the dipolar displacements in the surrounding octahedra, but insufficiently to result in dipole ordering. Mechanisms introducing small A-site lanthanide cations and incorporation of A-site vacancies to induce ferroelectricity and magnetism are presented. PMID:24421377

Cooling without contact in bilayer dipolar Fermi gases

NASA Astrophysics Data System (ADS)

Tanatar, Bilal; Renklioglu, Basak; Oktel, M. Ozgur

2016-05-01

We consider two parallel layers of dipolar ultracold Fermi gases at different temperatures and calculate the heat transfer between them. The effective interactions describing screening and correlation effects between the dipoles in a single layer are modelled within the Euler-Lagrange Fermi-hypernetted chain approximation. The random-phase approximation is employed for the interactions across the layers. We investigate the amount of transferred power between the layers as a function of the temperature difference. Energy transfer proceeds via the long-range dipole-dipole interactions. A simple thermal model is developed to investigate the feasibility of using the contactless sympathetic cooling of the ultracold polar atoms/molecules. Our calculations indicate that dipolar heat transfer is effective for typical polar molecule experiments and may be utilized as a cooling process. Supported by TUBA and TUBITAK (112T974).

Synthesis of Functionalized Pyrazoles via 1,3-Dipolar Cycloaddition of α-Diazo-β-ketophosphonates, Sufones and Esters with Electron-Deficient Alkenes.

PubMed

Baiju, T V; Namboothiri, Irishi N N

2017-10-01

1,3-Dipolar cycloaddition of diazo compounds with olefinic substrates is a promising atom-economic strategy for the construction of functionalized pyrazoles. Over the last few years, our group has been engaged in the synthesis of phosphonyl/sulfonylpyrazoles and pyrazole esters by employing Bestmann-Ohira Reagent (BOR) and its sulfur and ester analogs as 1,3-dipole precursors with various dipolarophiles. This account describes the novel synthetic methods developed in our laboratory, in the perspective of closely related work by others, for the synthesis of phosphonyl/sulfonylpyrazoles, pyrazole esters and the total synthesis of Withasomnine, a natural product, by using 1,3-dipolar cycloaddition as the key step. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Weyl Superfluidity in a Three-dimensional Dipolar Fermi Gas

NASA Astrophysics Data System (ADS)

Liu, Bo; Li, Xiaopeng; Yin, Lan; Liu, W. Vincent

2015-03-01

Weyl superconductivity or superfluidity, a fascinating topological state of matter, features novel phenomena such as emergent Weyl fermionic excitations and anomalies. Here we report that an anisotropic Weyl superfluid state can arise as a low temperature stable phase in a 3D dipolar Fermi gas. A crucial ingredient of our model is a direction-dependent two-body effective attraction generated by a rotating external field. Experimental signatures are predicted for cold gases in radio-frequency spectroscopy. The finite temperature phase diagram of this system is studied and the transition temperature of the Weyl superfluidity is found to be within the experimental scope for atomic dipolar Fermi gases. Work supported in part by U.S. ARO, AFOSR, DARPA-OLE-ARO, Charles E. Kaufman Foundation and The Pittsburgh Foundation, JQI-NSF-PFC, ARO-Atomtronics-MURI, and NSF of China.

How Different EEG References Influence Sensor Level Functional Connectivity Graphs

PubMed Central

Huang, Yunzhi; Zhang, Junpeng; Cui, Yuan; Yang, Gang; He, Ling; Liu, Qi; Yin, Guangfu

2017-01-01

Highlights: Hamming Distance is applied to distinguish the difference of functional connectivity networkThe orientations of sources are testified to influence the scalp Functional Connectivity Graph (FCG) from different references significantlyREST, the reference electrode standardization technique, is proved to have an overall stable and excellent performance in variable situations. The choice of an electroencephalograph (EEG) reference is a practical issue for the study of brain functional connectivity. To study how EEG reference influence functional connectivity estimation (FCE), this study compares the differences of FCE resulting from the different references such as REST (the reference electrode standardization technique), average reference (AR), linked mastoids (LM), and left mastoid references (LR). Simulations involve two parts. One is based on 300 dipolar pairs, which are located on the superficial cortex with a radial source direction. The other part is based on 20 dipolar pairs. In each pair, the dipoles have various orientation combinations. The relative error (RE) and Hamming distance (HD) between functional connectivity matrices of ideal recordings and that of recordings obtained with different references, are metrics to compare the differences of the scalp functional connectivity graph (FCG) derived from those two kinds of recordings. Lower RE and HD values imply more similarity between the two FCGs. Using the ideal recording (IR) as a standard, the results show that AR, LM and LR perform well only in specific conditions, i.e., AR performs stable when there is no upward component in sources' orientation. LR achieves desirable results when the sources' locations are away from left ear. LM achieves an indistinct difference with IR, i.e., when the distribution of source locations is symmetric along the line linking the two ears. However, REST not only achieves excellent performance for superficial and radial dipolar sources, but also achieves a stable and robust performance with variable source locations and orientations. Benefitting from the stable and robust performance of REST vs. other reference methods, REST might best recover the real FCG of EEG. Thus, REST based FCG may be a good candidate to compare the FCG of EEG based on different references from different labs. PMID:28725175

Magnetar-like emission in different neutron star classes

NASA Astrophysics Data System (ADS)

Rea, N.

2017-10-01

I will present new results on magnetar-like transient events in neutron stars having low dipolar fields or generally catalogued as normal radio pulsars or central compact objects. I will then present simulations of magnetic field evolution that might explain the apparently puzzling behaviour of these objects. Strong surface magnetic field might be an almost ubiquitous properties of pulsars, regardless their external dipolar magnetic field measured via their spin down properties.

Absence of Long-Range Order in a Triangular Spin System with Dipolar Interactions

NASA Astrophysics Data System (ADS)

Keleş, Ahmet; Zhao, Erhai

2018-05-01

The antiferromagnetic Heisenberg model on the triangular lattice is perhaps the best known example of frustrated magnets, but it orders at low temperatures. Recent density matrix renormalization group (DMRG) calculations find that the next nearest neighbor interaction J2 enhances the frustration, and it leads to a spin liquid for J2/J1∈(0.08 ,0.15 ). In addition, a DMRG study of a dipolar Heisenberg model with longer range interactions gives evidence for a spin liquid at a small dipole tilting angle θ ∈[0 ,1 0 ° ). In both cases, the putative spin liquid region appears to be small. Here, we show that for the triangular lattice dipolar Heisenberg model, a robust quantum paramagnetic phase exists in a surprisingly wide region, θ ∈[0 ,5 4 ° ) , for dipoles tilted along the lattice diagonal direction. We obtain the phase diagram of the model by functional renormalization group (RG), which treats all magnetic instabilities on equal footing. The quantum paramagnetic phase is characterized by a smooth continuous flow of vertex functions and spin susceptibility down to the lowest RG scale, in contrast to the apparent breakdown of RG flow in phases with stripe or spiral order. Our finding points to a promising direction to search for quantum spin liquids in ultracold dipolar molecules.

Magnetically controlled ferromagnetic swimmers

PubMed Central

Hamilton, Joshua K.; Petrov, Peter G.; Winlove, C. Peter; Gilbert, Andrew D.; Bryan, Matthew T.; Ogrin, Feodor Y.

2017-01-01

Microscopic swimming devices hold promise for radically new applications in lab-on-a-chip and microfluidic technology, diagnostics and drug delivery etc. In this paper, we demonstrate the experimental verification of a new class of autonomous ferromagnetic swimming devices, actuated and controlled solely by an oscillating magnetic field. These devices are based on a pair of interacting ferromagnetic particles of different size and different anisotropic properties joined by an elastic link and actuated by an external time-dependent magnetic field. The net motion is generated through a combination of dipolar interparticle gradient forces, time-dependent torque and hydrodynamic coupling. We investigate the dynamic performance of a prototype (3.6 mm) of the ferromagnetic swimmer in fluids of different viscosity as a function of the external field parameters (frequency and amplitude) and demonstrate stable propulsion over a wide range of Reynolds numbers. We show that the direction of swimming has a dependence on both the frequency and amplitude of the applied external magnetic field, resulting in robust control over the speed and direction of propulsion. This paves the way to fabricating microscale devices for a variety of technological applications requiring reliable actuation and high degree of control. PMID:28276490

Magnetically controlled ferromagnetic swimmers

NASA Astrophysics Data System (ADS)

Hamilton, Joshua K.; Petrov, Peter G.; Winlove, C. Peter; Gilbert, Andrew D.; Bryan, Matthew T.; Ogrin, Feodor Y.

2017-03-01

Microscopic swimming devices hold promise for radically new applications in lab-on-a-chip and microfluidic technology, diagnostics and drug delivery etc. In this paper, we demonstrate the experimental verification of a new class of autonomous ferromagnetic swimming devices, actuated and controlled solely by an oscillating magnetic field. These devices are based on a pair of interacting ferromagnetic particles of different size and different anisotropic properties joined by an elastic link and actuated by an external time-dependent magnetic field. The net motion is generated through a combination of dipolar interparticle gradient forces, time-dependent torque and hydrodynamic coupling. We investigate the dynamic performance of a prototype (3.6 mm) of the ferromagnetic swimmer in fluids of different viscosity as a function of the external field parameters (frequency and amplitude) and demonstrate stable propulsion over a wide range of Reynolds numbers. We show that the direction of swimming has a dependence on both the frequency and amplitude of the applied external magnetic field, resulting in robust control over the speed and direction of propulsion. This paves the way to fabricating microscale devices for a variety of technological applications requiring reliable actuation and high degree of control.

NCN-Coordinating Ligands based on Pyrene Structure with Potential Application in Organic Electronics.

PubMed

Zych, Dawid; Kurpanik, Aneta; Slodek, Aneta; Maroń, Anna; Pająk, Michał; Szafraniec-Gorol, Grażyna; Matussek, Marek; Krompiec, Stanisław; Schab-Balcerzak, Ewa; Kotowicz, Sonia; Siwy, Mariola; Smolarek, Karolina; Maćkowski, Sebastian; Danikiewicz, Witold

2017-11-07

Five novel derivatives of pyrene, substituted at positions 1,3,6,8 with 4-(2,2-dimethylpropyloxy)pyridine (P1), 4-decyloxypyridine (P2), 4-pentylpyridine (P3), 1-decyl-1,2,3-triazole (P4), and 1-benzyl-1,2,3-triazole (P5), are obtained through a Suzuki-Miyaura cross-coupling reaction or Cu I -catalyzed 1,3-dipolar cycloaddition reaction, respectively, and characterized thoroughly. TGA measurements reveal the high thermal stability of the compounds. Pyrene derivatives P1-P5 all show photoluminescence (PL) quantum yields (Φ) of approximately 75 % in solution. Solid-state photo- and electroluminescence characteristics of selected compounds as organic light-emitting diodes are tested. In the guest-host configuration, two matrixes, that is, poly(N-vinylcarbazole) (PVK) and a binary matrix consisting of PVK and 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole (PBD) (50:50 wt %), are applied. The diodes show red, green, or blue electroluminescence, depending on both the compound chemical structure and the actual device architecture. In addition, theoretical studies (DFT and TD-DFT) provide a deeper understanding of the experimental results. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The natural oscillation of two types of ENSO events based on analyses of CMIP5 model control runs

NASA Astrophysics Data System (ADS)

Xu, Kang; Su, Jingzhi; Zhu, Congwen

2014-07-01

The eastern- and central-Pacific El Niño-Southern Oscillation (EP- and CP-ENSO) have been found to be dominant in the tropical Pacific Ocean, and are characterized by interannual and decadal oscillation, respectively. In the present study, we defined the EP- and CP-ENSO modes by singular value decomposition (SVD) between SST and sea level pressure (SLP) anomalous fields. We evaluated the natural features of these two types of ENSO modes as simulated by the pre-industrial control runs of 20 models involved in phase five of the Coupled Model Intercomparison Project (CMIP5). The results suggested that all the models show good skill in simulating the SST and SLP anomaly dipolar structures for the EP-ENSO mode, but only 12 exhibit good performance in simulating the tripolar CP-ENSO modes. Wavelet analysis suggested that the ensemble principal components in these 12 models exhibit an interannual and multi-decadal oscillation related to the EP- and CP-ENSO, respectively. Since there are no changes in external forcing in the pre-industrial control runs, such a result implies that the decadal oscillation of CP-ENSO is possibly a result of natural climate variability rather than external forcing.

Flagellum synchronization inhibits large-scale hydrodynamic instabilities in sperm suspensions

NASA Astrophysics Data System (ADS)

Schöller, Simon F.; Keaveny, Eric E.

2016-11-01

Sperm in suspension can exhibit large-scale collective motion and form coherent structures. Our picture of such coherent motion is largely based on reduced models that treat the swimmers as self-locomoting rigid bodies that interact via steady dipolar flow fields. Swimming sperm, however, have many more degrees of freedom due to elasticity, have a more exotic shape, and generate spatially-complex, time-dependent flow fields. While these complexities are known to lead to phenomena such as flagellum synchronization and attraction, how these effects impact the overall suspension behaviour and coherent structure formation is largely unknown. Using a computational model that captures both flagellum beating and elasticity, we simulate suspensions on the order of 103 individual swimming sperm cells whose motion is coupled through the surrounding Stokesian fluid. We find that the tendency for flagella to synchronize and sperm to aggregate inhibits the emergence of the large-scale hydrodynamic instabilities often associated with active suspensions. However, when synchronization is repressed by adding noise in the flagellum actuation mechanism, the picture changes and the structures that resemble large-scale vortices appear to re-emerge. Supported by an Imperial College PhD scholarship.

A molecular quantum spin network controlled by a single qubit.

PubMed

Schlipf, Lukas; Oeckinghaus, Thomas; Xu, Kebiao; Dasari, Durga Bhaktavatsala Rao; Zappe, Andrea; de Oliveira, Felipe Fávaro; Kern, Bastian; Azarkh, Mykhailo; Drescher, Malte; Ternes, Markus; Kern, Klaus; Wrachtrup, Jörg; Finkler, Amit

2017-08-01

Scalable quantum technologies require an unprecedented combination of precision and complexity for designing stable structures of well-controllable quantum systems on the nanoscale. It is a challenging task to find a suitable elementary building block, of which a quantum network can be comprised in a scalable way. We present the working principle of such a basic unit, engineered using molecular chemistry, whose collective control and readout are executed using a nitrogen vacancy (NV) center in diamond. The basic unit we investigate is a synthetic polyproline with electron spins localized on attached molecular side groups separated by a few nanometers. We demonstrate the collective readout and coherent manipulation of very few (≤ 6) of these S = 1/2 electronic spin systems and access their direct dipolar coupling tensor. Our results show that it is feasible to use spin-labeled peptides as a resource for a molecular qubit-based network, while at the same time providing simple optical readout of single quantum states through NV magnetometry. This work lays the foundation for building arbitrary quantum networks using well-established chemistry methods, which has many applications ranging from mapping distances in single molecules to quantum information processing.

Photoinduced Bioorthogonal 1,3-Dipolar Poly-cycloaddition Promoted by Oxyanionic Substrates for Spatiotemporal Operation of Molecular Glues.

PubMed

Hatano, Junichi; Okuro, Kou; Aida, Takuzo

2016-01-04

PGlue(PZ), a pyrazoline (PZ)-based fluorescent adhesive which can be generated spatiotemporally in living systems, was developed. Since PGlue(PZ) carries many guanidinium ion (Gu(+)) pendants, it strongly adheres to various oxyanionic substrates through a multivalent salt-bridge interaction. PGlue(PZ) is given by bioorthogonal photopolymerization of a Gu(+)-appended monomer (Glue(TZ)), bearing tetrazole (TZ) and olefinic termini. Upon exposure to UV light, Glue(TZ) transforms into a nitrileimine (NI) intermediate (Glue(NI)), which is eligible for 1,3-dipolar polycycloaddition. However, Glue(NI) in aqueous media can concomitantly be deactivated into Glue(WA) by the addition of water, and the polymerization hardly occurs unless Glue(NI) is concentrated. We found that, even under high dilution, Glue(NI) is concentrated on oxyanionic substrates to a sufficient level for the polymerization, so that their surfaces can be point-specifically functionalized with PGlue(PZ) by the use of a focused beam of UV light. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Observation of discrete time-crystalline order in a disordered dipolar many-body system

NASA Astrophysics Data System (ADS)

Choi, Soonwon; Choi, Joonhee; Landig, Renate; Kucsko, Georg; Zhou, Hengyun; Isoya, Junichi; Jelezko, Fedor; Onoda, Shinobu; Sumiya, Hitoshi; Khemani, Vedika; von Keyserlingk, Curt; Yao, Norman; Demler, Eugene; Lukin, Mikhail

2017-04-01

The interplay of periodic driving, disorder, and strong interactions has recently been predicted to result in exotic ``time crystalline'' phases, which spontaneously break the discrete time translation symmetry of the underlying drive. Here, we report the experimental observation of such discrete time crystalline order in a driven, disordered ensemble of dipolar spin impurities in diamond at room temperature. We observe long lived temporal correlations at integer multiples of the fundamental driving period, experimentally identify the phase boundary and find that the temporal order is protected by strong interactions; this order is remarkably stable against perturbations, even in the presence of slow thermalization. We provide a theoretical description of approximate Floquet eigenstates of the system based on product state ansatz and predict the phase boundary, which is in qualitative agreement with our observations. Our work opens the door to exploring dynamical phases of matter and controlling interacting, disordered many body systems. NSF, CUA, NSSEFF, ARO MURI, Moore Foundation.

Multipolar second-harmonic generation by Mie-resonant dielectric nanoparticles

NASA Astrophysics Data System (ADS)

Smirnova, Daria; Smirnov, Alexander I.; Kivshar, Yuri S.

2018-01-01

By combining analytical and numerical approaches, we study resonantly enhanced second-harmonic generation by individual high-index dielectric nanoparticles made of centrosymmetric materials. Considering both bulk and surface nonlinearities, we describe second-harmonic nonlinear scattering from a silicon nanoparticle optically excited in the vicinity of the magnetic and electric dipolar resonances. We discuss the contributions of different nonlinear sources and the effect of the low-order optical Mie modes on the characteristics of the generated far field. We demonstrate that the multipolar expansion of the radiated field is dominated by dipolar and quadrupolar modes (two axially symmetric electric quadrupoles, an electric dipole, and a magnetic quadrupole) and the interference of these modes can ensure directivity of the nonlinear scattering. The developed multipolar analysis can be instructive for interpreting the far-field measurements of the nonlinear scattering and it provides prospective insights into a design of complementary metal-oxide-semiconductor compatible nonlinear nanoantennas fully integrated with silicon-based photonic circuits, as well as methods of nonlinear diagnostics.

Self-replication with magnetic dipolar colloids

NASA Astrophysics Data System (ADS)

Dempster, Joshua M.; Zhang, Rui; Olvera de la Cruz, Monica

2015-10-01

Colloidal self-replication represents an exciting research frontier in soft matter physics. Currently, all reported self-replication schemes involve coating colloidal particles with stimuli-responsive molecules to allow switchable interactions. In this paper, we introduce a scheme using ferromagnetic dipolar colloids and preprogrammed external magnetic fields to create an autonomous self-replication system. Interparticle dipole-dipole forces and periodically varying weak-strong magnetic fields cooperate to drive colloid monomers from the solute onto templates, bind them into replicas, and dissolve template complexes. We present three general design principles for autonomous linear replicators, derived from a focused study of a minimalist sphere-dimer magnetic system in which single binding sites allow formation of dimeric templates. We show via statistical models and computer simulations that our system exhibits nonlinear growth of templates and produces nearly exponential growth (low error rate) upon adding an optimized competing electrostatic potential. We devise experimental strategies for constructing the required magnetic colloids based on documented laboratory techniques. We also present qualitative ideas about building more complex self-replicating structures utilizing magnetic colloids.

A statistical study of near-Earth magnetotail evolution during substorms and pseudosubstorms with THEMIS data

NASA Astrophysics Data System (ADS)

Fukui, K.; Machida, S.; Miyashita, Y.; Yoshizumi, M.; Angelopoulos, V.

2017-12-01

Substorms and pseudosubstorms (pseudobreakups) are very similar phenomena. In terms of auroral morphology, pseudosubstorms are generally more localized and more short-lived, compared with substorms, and are not accompanied by poleward expansion. We examined auroral development for events from November 2007 through April 2010, using data from THEMIS all-sky imagers. We defined events accompanied and not accompanied by poleward expansion as substorms and pseudosubstorms, respectively. To understand the cause of auroral development, we investigated temporal and spatial development of the near-Earth magnetotail during substorms and pseudosubstorms, based on superposed epoch analysis of THEMIS data. We find that Vx begins to increase at -9.5 >X(GSM)>-11.5 Re around onset for both substorms and pseudosubstorms. This seems to be due to earthward flows caused by magnetic reconnection. The northward Bz also increases around onset at -9.5 >X>-10.5 Re both substorms and pseudosubstorms. The amount and rate of Bz change are larger for substorms than for pseudosubstorms. In the earthward (-7.5 >X>-9.5 Re) and tailward (-10.5 >X>-12.5 Re) regions, Bz increases substantially for substorms, whereas it does not increase very much for pseudosubstorms. These results indicate that dipolarization is weaker for pseudosubstorms than for substorms, and the dipolarization region does not spread extensively for pseudosubstorms. We, therefore, suggest that current disruption related to dipolarization does not develop tailward and hence auroral poleward expansion does not occur for pseudosubstorms. Meanwhile, the plasma and magnetic pressures increase at -6.5 >X>-7.5 Re after onset in association with dipolarization, particularly for substorms. The total pressure (the sum of the plasma and magnetic pressures) prior to the onset is larger in that region for substorms than for pseudosubstorms. At -7.5 >X>-8.5 Re the total pressure hardly differ between substorms and pseudosubstorms. Thus we conclude that the spatial gradient of the total pressure is a key that determines whether the current disruption takes place, that is, whether initial activation develops into a substorm or into a subsiding pseudosubstorm.

Low temperatures shear viscosity of a two-component dipolar Fermi gas with unequal population

NASA Astrophysics Data System (ADS)

Darsheshdar, E.; Yavari, H.; Zangeneh, Z.

2016-07-01

By using the Green's functions method and linear response theory we calculate the shear viscosity of a two-component dipolar Fermi gas with population imbalance (spin polarized) in the low temperatures limit. In the strong-coupling Bose-Einstein condensation (BEC) region where a Feshbach resonance gives rise to tightly bound dimer molecules, a spin-polarized Fermi superfluid reduces to a simple Bose-Fermi mixture of Bose-condensed dimers and the leftover unpaired fermions (atoms). The interactions between dimer-atom, dimer-dimer, and atom-atom take into account to the viscous relaxation time (τη) . By evaluating the self-energies in the ladder approximation we determine the relaxation times due to dimer-atom (τDA) , dimer-dimer (τcDD ,τdDD) , and atom-atom (τAA) interactions. We will show that relaxation rates due to these interactions τDA-1 ,τcDD-1, τdDD-1, and τAA-1 have T2, T4, e - E /kB T (E is the spectrum of the dimer atoms), and T 3 / 2 behavior respectively in the low temperature limit (T → 0) and consequently, the atom-atom interaction plays the dominant role in the shear viscosity in this rang of temperatures. For small polarization (τDA ,τAA ≫τcDD ,τdDD), the low temperatures shear viscosity is determined by contact interaction between dimers and the shear viscosity varies as T-5 which has the same behavior as the viscosity of other superfluid systems such as superfluid neutron stars, and liquid helium.

On the Acceleration and Anisotropy of Ions Within Magnetotail Dipolarizing Flux Bundles

NASA Astrophysics Data System (ADS)

Zhou, Xu-Zhi; Runov, Andrei; Angelopoulos, Vassilis; Artemyev, Anton V.; Birn, Joachim

2018-01-01

Dipolarizing flux bundles (DFBs), earthward propagating structures with enhanced northward magnetic field Bz, are usually believed to carry a distinctly different plasma population from that in the ambient magnetotail plasma sheet. The ion distribution functions within the DFB, however, have been recently found to be largely controlled by the ion adiabaticity parameter κ in the ambient plasma sheet outside the DFB. According to these observations, the ambient κ values of 2-3 usually correspond to a strong perpendicular anisotropy of suprathermal ions within the DFB, whereas for lower κ values the DFB ions become more isotropic. Here we utilize a simple, test particle model to explore the nature of the anisotropy and its dependence on the ambient κ values. We find that the anisotropy originates from successive ion reflections and reentries to the DFB, during which the ions are consecutively accelerated in the perpendicular direction by the DFB-associated electric field. This consecutive acceleration may be interrupted, however, when magnetic field lines are highly curved in the ambient plasma sheet. In this case, the ion trajectories become stochastic outside the DFB, which makes the reflected ions less likely to return to the DFB for another cycle of acceleration; as a consequence, the perpendicular ion anisotropy does not appear. Given that the DFB ions are a free energy source for instabilities when they are injected toward Earth, our simple model (that reproduces most observational features on the anisotropic DFB ion distributions) may shed new lights on the coupling process between magnetotail and inner magnetosphere.

Multipolar Kondo effect in a S10-P32 mixture of 173Yb atoms

NASA Astrophysics Data System (ADS)

Kuzmenko, Igor; Kuzmenko, Tetyana; Avishai, Yshai; Jo, Gyu-Boong

2018-02-01

Whereas in the familiar Kondo effect the exchange interaction is dipolar, there are systems in which the exchange interaction is multipolar, as has been realized in a recent experiment. Here, we study multipolar Kondo effect in a Fermi gas of cold 173Yb atoms. Making use of different ac polarizabilities of the electronic ground state Yb (S10 ) and the long-lived metastable state Yb*(P32 ), it is suggested that the latter atoms can be localized and serve as a dilute concentration of magnetic impurities while the former ones remain itinerant. The exchange mechanism between the itinerant Yb and the localized Yb* atoms is analyzed and shown to be antiferromagnetic. The quadrupole and octupole interactions act to enhance the Kondo temperature TK that is found to be experimentally accessible. The bare exchange Hamiltonian needs to be decomposed into dipole (d), quadrupole (q), and octupole (o) interactions in order to retain its form under renormalization group (RG) analysis, in which the corresponding exchange constants (λd,λq, and λo) flow independently. Numerical solution of the RG scaling equations reveals a few finite fixed points. Arguments are presented that the Fermi-liquid fixed point at low temperature is unstable, indicating that the impurity is overscreened, which suggests a non-Fermi-liquid phase. The impurity contributions to the specific heat, entropy, and the magnetic susceptibility are calculated in the weak coupling regime (T ≫TK ), and are compared with the analogous results obtained for the standard case of dipolar exchange interaction (the s -d Hamiltonian).

On the use of Schwarz-Christoffel conformal mappings to the grid generation for global ocean models

NASA Astrophysics Data System (ADS)

Xu, S.; Wang, B.; Liu, J.

2015-10-01

In this article we propose two grid generation methods for global ocean general circulation models. Contrary to conventional dipolar or tripolar grids, the proposed methods are based on Schwarz-Christoffel conformal mappings that map areas with user-prescribed, irregular boundaries to those with regular boundaries (i.e., disks, slits, etc.). The first method aims at improving existing dipolar grids. Compared with existing grids, the sample grid achieves a better trade-off between the enlargement of the latitudinal-longitudinal portion and the overall smooth grid cell size transition. The second method addresses more modern and advanced grid design requirements arising from high-resolution and multi-scale ocean modeling. The generated grids could potentially achieve the alignment of grid lines to the large-scale coastlines, enhanced spatial resolution in coastal regions, and easier computational load balance. Since the grids are orthogonal curvilinear, they can be easily utilized by the majority of ocean general circulation models that are based on finite difference and require grid orthogonality. The proposed grid generation algorithms can also be applied to the grid generation for regional ocean modeling where complex land-sea distribution is present.

Feasibility of Equivalent Dipole Models for Electroencephalogram-Based Brain Computer Interfaces.

PubMed

Schimpf, Paul H

2017-09-15

This article examines the localization errors of equivalent dipolar sources inverted from the surface electroencephalogram in order to determine the feasibility of using their location as classification parameters for non-invasive brain computer interfaces. Inverse localization errors are examined for two head models: a model represented by four concentric spheres and a realistic model based on medical imagery. It is shown that the spherical model results in localization ambiguity such that a number of dipolar sources, with different azimuths and varying orientations, provide a near match to the electroencephalogram of the best equivalent source. No such ambiguity exists for the elevation of inverted sources, indicating that for spherical head models, only the elevation of inverted sources (and not the azimuth) can be expected to provide meaningful classification parameters for brain-computer interfaces. In a realistic head model, all three parameters of the inverted source location are found to be reliable, providing a more robust set of parameters. In both cases, the residual error hypersurfaces demonstrate local minima, indicating that a search for the best-matching sources should be global. Source localization error vs. signal-to-noise ratio is also demonstrated for both head models.

Molecular orientation in a dielectric liquid-vapor interphase

NASA Astrophysics Data System (ADS)

Chacón, E.; Mederos, L.; Navascués, G.; Tarazona, P.

1985-04-01

The density functional theory of Chacón et al. is used to study the molecular orientation in an interphase of a weak dipolar fluid. Explicit expressions are obtained using standard perturbation techniques. Molecular orientation, local susceptibility, and the Gibbsean surface susceptibility are evaluated for a Stockmayer model of dipolar fluid. The effect of the surface structure on the bulk ferroelectric transition is discussed in the light of the present theory and the numerical results.

Observation of plasmonic dipolar anti-bonding mode in silver nanoring structures.

PubMed

Ye, Jian; Van Dorpe, Pol; Lagae, Liesbet; Maes, Guido; Borghs, Gustaaf

2009-11-18

We report on a clear experimental observation of the plasmonic dipolar anti-bonding resonance in silver nanorings. The data can be explained effectively by the plasmon hybridization model, which is confirmed by the numerical calculations of the electromagnetic field and surface charge distribution profiles. The experimental demonstration of the plasmon hybridization model indicates its usefulness as a valuable tool to understand, design and predict optical properties of metallic nanostructures.

Observation of plasmonic dipolar anti-bonding mode in silver nanoring structures

NASA Astrophysics Data System (ADS)

Ye, Jian; Van Dorpe, Pol; Lagae, Liesbet; Maes, Guido; Borghs, Gustaaf

2009-11-01

We report on a clear experimental observation of the plasmonic dipolar anti-bonding resonance in silver nanorings. The data can be explained effectively by the plasmon hybridization model, which is confirmed by the numerical calculations of the electromagnetic field and surface charge distribution profiles. The experimental demonstration of the plasmon hybridization model indicates its usefulness as a valuable tool to understand, design and predict optical properties of metallic nanostructures.

Arrays of dipolar molecular rotors in Tris(o-phenylenedioxy) cyclotriphosphazene.

PubMed

Zhao, Ke; Dron, Paul I; Kaleta, Jiří; Rogers, Charles T; Michl, Josef

2014-01-01

Regular two-dimensional or three-dimensional arrays of mutually interacting dipolar molecular rotors represent a worthy synthetic objective. Their dielectric properties, including possible collective behavior, will be a sensitive function of the location of the rotors, the orientation of their axes, and the size of their dipoles. Host-guest chemistry is one possible approach to gaining fine control over these factors. We describe the progress that has been achieved in recent years using tris (o-phenylenedioxy)cyclotriphosphazene as a host and a series of rod-shaped dipolar molecular rotors as guests. Structures of both surface and bulk inclusion compounds have been established primarily by solid-state nuclear magnetic resonance (NMR) and powder X-ray diffraction (XRD) techniques. Low-temperature dielectric spectroscopy revealed rotational barriers as low as 1.5 kcal/mol, but no definitive evidence for collective behavior has been obtained so far.

Classical and quantum filaments in the ground state of trapped dipolar Bose gases

NASA Astrophysics Data System (ADS)

Cinti, Fabio; Boninsegni, Massimo

2017-07-01

We study, by quantum Monte Carlo simulations, the ground state of a harmonically confined dipolar Bose gas with aligned dipole moments and with the inclusion of a repulsive two-body potential of varying range. Two different limits can clearly be identified, namely, a classical one in which the attractive part of the dipolar interaction dominates and the system forms an ordered array of parallel filaments and a quantum-mechanical one, wherein filaments are destabilized by zero-point motion, and eventually the ground state becomes a uniform cloud. The physical character of the system smoothly evolves from classical to quantum mechanical as the range of the repulsive two-body potential increases. An intermediate regime is observed in which ordered filaments are still present, albeit forming different structures from the ones predicted classically; quantum-mechanical exchanges of indistinguishable particles across different filaments allow phase coherence to be established, underlying a global superfluid response.

Critical Time Crystals in Dipolar Systems

NASA Astrophysics Data System (ADS)

Ho, Wen Wei; Choi, Soonwon; Lukin, Mikhail D.; Abanin, Dmitry A.

2017-07-01

We analyze the quantum dynamics of periodically driven, disordered systems in the presence of long-range interactions. Focusing on the stability of discrete time crystalline (DTC) order in such systems, we use a perturbative procedure to evaluate its lifetime. For 3D systems with dipolar interactions, we show that the corresponding decay is parametrically slow, implying that robust, long-lived DTC order can be obtained. We further predict a sharp crossover from the stable DTC regime into a regime where DTC order is lost, reminiscent of a phase transition. These results are in good agreement with the recent experiments utilizing a dense, dipolar spin ensemble in diamond [Nature (London) 543, 221 (2017), 10.1038/nature21426]. They demonstrate the existence of a novel, critical DTC regime that is stabilized not by many-body localization but rather by slow, critical dynamics. Our analysis shows that the DTC response can be used as a sensitive probe of nonequilibrium quantum matter.

Gold (I)-Catalyzed Diastereo- and Enantioselective 1,3-Dipolar Cycloaddition and Mannich Reactions of Azlactones

PubMed Central

Melhado, Asa D.; Amarante, Giovanni W.; Wang, Z. Jane; Luparia, Marco; Toste, F. Dean

2011-01-01

Azlactones participate in stereoselective reactions with electron-deficient alkenes and N-sulfonyl aldimines to give products of 1,3-dipolar cycloaddition and Mannich addition reactions respectively. Both of these reactions proceed with good to excellent diastereo- and enantioselectivity using a single class of gold-catalysts, namely C2-symmetric bis(phosphinegold(I) carboxylate)complexes. The development of the azlactone Mannich reaction to provide fully protected anti-α,β-diamino acid derivatives is described. 1,3-Dipolar cycloaddition reactions of several acyclic 1,2-disubstituted alkenes, and the chemistry of the resultant cycloadducts, are examined to probe the stereochemical course of this reaction. Reaction kinetics and tandem MS studies of both the cycloaddition and Mannich reactions are reported. These studies support a mechanism in which the gold complexes catalyze addition reactions through nucleophile activation rather than the more typical activation of the electrophilic reaction component. PMID:21341677

Microscopic model of quasiparticle wave packets in superfluids, superconductors, and paired Hall states.

PubMed

Parameswaran, S A; Kivelson, S A; Shankar, R; Sondhi, S L; Spivak, B Z

2012-12-07

We study the structure of Bogoliubov quasiparticles, bogolons, the fermionic excitations of paired superfluids that arise from fermion (BCS) pairing, including neutral superfluids, superconductors, and paired quantum Hall states. The naive construction of a stationary quasiparticle in which the deformation of the pair field is neglected leads to a contradiction: it carries a net electrical current even though it does not move. However, treating the pair field self-consistently resolves this problem: in a neutral superfluid, a dipolar current pattern is associated with the quasiparticle for which the total current vanishes. When Maxwell electrodynamics is included, as appropriate to a superconductor, this pattern is confined over a penetration depth. For paired quantum Hall states of composite fermions, the Maxwell term is replaced by a Chern-Simons term, which leads to a dipolar charge distribution and consequently to a dipolar current pattern.

Quantum mechanical identification of quadrupolar plasmonic excited states in silver nanorods

DOE PAGES

Gieseking, Rebecca L.; Ratner, Mark A.; Schatz, George C.

2016-10-27

Quadrupolar plasmonic modes in noble metal nanoparticles have gained interest in recent years for various sensing applications. Although quantum mechanical studies have shown that dipolar plasmons can be modeled in terms of excited states where several to many excitations contribute coherently to the transition dipole moment, new approaches are needed to identify the quadrupolar plasmonic states. We show that quadrupolar states in Ag nanorods can be identified using the semiempirical INDO/SCI approach by examining the quadrupole moment of the transition density. The main longitudinal quadrupolar states occur at higher energies than the longitudinal dipolar states, in agreement with previous classicalmore » electrodynamics results, and have collective plasmonic character when the nanorods are sufficiently long. In conclusion, the ability to identify these states will make it possible to evaluate the differences between dipolar and quadrupolar plasmons that are relevant for sensing applications.« less

Design of Co/Pd multilayer system with antiferromagnetic-to-ferromagnetic phase transition

NASA Astrophysics Data System (ADS)

Thiele, Jan-Ulrich

2009-03-01

Among the known magnetic material systems there are only very few examples of materials that undergo a temperature dependent antiferromagnetic-to-ferromagnetic phase transition, and of these only the chemically ordered alloy FeRh exhibits this transition near room temperature [1, 2]. Here we present a perpendicular anisotropy multilayer structure that mimics FeRh. The basic idea is to use two stacks of Co/Pd multilayers with large perpendicular magnetic anisotropy and high Curie temperature, TC, separated by a layer providing antiferromagnetic coupling, and a CoNi/Pd multilayer with perpendicular anisotropy with a lower TC, interlayer, in the range of the desired AF-FM transition temperature, TAF-FM. At room temperature this system behaves as two antiferromagnetically coupled layers with a low perpendicular remanent magnetic moment. As the temperature is raised to approach TC, interlayer the magnetization of the interlayer is gradually reduced to zero, and consequently its coupling strength is reduced. Eventually, the effective coupling between the two high-KU, high-TC layers becomes dominated by their dipolar fields, resulting in a parallel alignment of their moments and a net remanent magnetic moment equal to the sum of the moments of the two high-TC layers [2]. [4pt] [1] J. S. Kouvel and C. C. Hartelius, J. Appl. Phys. 33 (1962) p1343 [0pt] [2] J.-U. Thiele, E. E. Fullerton, S. Maat, Appl. Phys. Lett. 82 (2003) p2859 [0pt] [3] J.-U. Thiele. T. Hauet. O. Hellwig, Appl. Phys. Lett. 92 (2008) 242502.

CIDME: Short distances measured with long chirp pulses.

PubMed

Doll, Andrin; Qi, Mian; Godt, Adelheid; Jeschke, Gunnar

2016-12-01

Frequency-swept pulses have recently been introduced as pump pulses into double electron-electron resonance (DEER) experiments. A limitation of this approach is that the pump pulses need to be short in comparison to dipolar evolution periods. The "chirp-induced dipolar modulation enhancement" (CIDME) pulse sequence introduced in this work circumvents this limitation by means of longitudinal storage during the application of one single or two consecutive pump pulses. The resulting six-pulse sequence is closely related to the five-pulse "relaxation-induced dipolar modulation enhancement" (RIDME) pulse sequence: While dipolar modulation in RIDME is due to stochastic spin flips during longitudinal storage, modulation in CIDME is due to the pump pulse during longitudinal storage. Experimentally, CIDME is examined for Gd-Gd and nitroxide-nitroxide distance determination using a high-power Q-band spectrometer. Since longitudinal storage results in a 50% signal loss, comparisons between DEER using short chirp pump pulses of 64ns duration and CIDME using longer pump pulses are in favor of DEER. While the lower sensitivity restrains the applicability of CIDME for routine distance determination on high-power spectrometers, this result is not to be generalized to spectrometers having lower power and to specialized "non-routine" applications or different types of spin labels. In particular, the advantage of prolonged CIDME pump pulses is demonstrated for experiments at large frequency offset between the pumped and observed spins. At a frequency separation of 1GHz, where broadening due to dipolar pseudo-secular contributions becomes largely suppressed, a Gd-Gd modulation depth larger than 10% is achieved. Moreover, a CIDME experiment at deliberately reduced power underlines the potential of the new technique for spectrometers with lower power, as often encountered at higher microwave frequencies. With longitudinal storage times T below 10μs, however, CIDME appears rather susceptible to artifacts. For nitroxide-nitroxide experiments, these currently inhibit a faithful data analysis. To facilitate further developments, the artifacts are characterized experimentally. In addition, effects that are specific to the high spin of S=7/2 Gd-centers are examined. Herein, population transfer within the observer spin's multiplet due to the pump pulse as well as excitation of dipolar harmonics are discussed. Copyright © 2016 Elsevier Inc. All rights reserved.

Modeling and visualization of carrier motion in organic films by optical second harmonic generation and Maxwell-displacement current

NASA Astrophysics Data System (ADS)

Iwamoto, Mitsumasa; Manaka, Takaaki; Taguchi, Dai

2015-09-01

The probing and modeling of carrier motions in materials as well as in electronic devices is a fundamental research subject in science and electronics. According to the Maxwell electromagnetic field theory, carriers are a source of electric field. Therefore, by probing the dielectric polarization caused by the electric field arising from moving carriers and dipoles, we can find a way to visualize the carrier motions in materials and in devices. The techniques used here are an electrical Maxwell-displacement current (MDC) measurement and a novel optical method based on the electric field induced optical second harmonic generation (EFISHG) measurement. The MDC measurement probes changes of induced charge on electrodes, while the EFISHG probes nonlinear polarization induced in organic active layers due to the coupling of electron clouds of molecules and electro-magnetic waves of an incident laser beam in the presence of a DC field caused by electrons and holes. Both measurements allow us to probe dynamical carrier motions in solids through the detection of dielectric polarization phenomena originated from dipolar motions and electron transport. In this topical review, on the basis of Maxwell’s electro-magnetism theory of 1873, which stems from Faraday’s idea, the concept for probing electron and hole transport in solids by using the EFISHG is discussed in comparison with the conventional time of flight (TOF) measurement. We then visualize carrier transit in organic devices, i.e. organic field effect transistors, organic light emitting diodes, organic solar cells, and others. We also show that visualizing an EFISHG microscopic image is a novel way for characterizing anisotropic carrier transport in organic thin films. We also discuss the concept of the detection of rotational dipolar motions in monolayers by means of the MDC measurement, which is capable of probing the change of dielectric spontaneous polarization formed by dipoles in organic monolayers. Finally we conclude that the ideas and experiments on EFISHG and MDC lead to a novel way of analyzing dynamical motions of electrons, holes, and dipoles in solids, and thus are available in organic electronic device application.

The roles of molecular structure and effective optical symmetry in evolving dipolar chromophoric building blocks to potent octopolar nonlinear optical chromophores.

PubMed

Ishizuka, Tomoya; Sinks, Louise E; Song, Kai; Hung, Sheng-Ting; Nayak, Animesh; Clays, Koen; Therien, Michael J

2011-03-09

A series of mono-, bis-, tris-, and tetrakis(porphinato)zinc(II) (PZn)-elaborated ruthenium(II) bis(terpyridine) (Ru) complexes have been synthesized in which an ethyne unit connects the macrocycle meso carbon atom to terpyridyl (tpy) 4-, 4'-, and 4''-positions. These supermolecular chromophores, based on the ruthenium(II) [5-(4'-ethynyl-(2,2';6',2''-terpyridinyl))-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2''-terpyridine)(2+) bis-hexafluorophosphate (RuPZn) archetype, evince strong mixing of the PZn-based oscillator strength with ruthenium terpyridyl charge resonance bands. Potentiometric and linear absorption spectroscopic data indicate that for structures in which multiple PZn moieties are linked via ethynes to a [Ru(tpy)(2)](2+) core, little electronic coupling is manifest between PZn units, regardless of whether they are located on the same or opposite tpy ligand. Congruent with these experiments, pump-probe transient absorption studies suggest that the individual RuPZn fragments of these structures exhibit, at best, only modest excited-state electronic interactions that derive from factors other than the dipole-dipole interactions of these strong oscillators; this approximate independent character of the component RuPZn oscillators enables fabrication of nonlinear optical (NLO) multipoles with extraordinary hyperpolarizabilities. Dynamic hyperpolarizability (β(λ)) values and depolarization ratios (ρ) were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at an incident irradiation wavelength (λ(inc)) of 1300 nm. The depolarization ratio data provide an experimental measure of chromophore optical symmetry; appropriate coupling of multiple charge-transfer oscillators produces structures having enormous averaged hyperpolarizabilities (β(HRS) values), while evolving the effective chromophore symmetry from purely dipolar (e.g., Ru(tpy)[4-(Zn-porphyrin)ethynyl-tpy](PF(6))(2), β(HRS) = 1280 × 10(-30) esu, ρ = 3.8; Ru(tpy)[4'-(Zn-porphyrin)ethynyl-tpy](PF(6))(2), β(HRS) = 2100 × 10(-30) esu, ρ = 3.8) to octopolar (e.g., Ru[4,4''-bis(Zn-porphyrin)ethynyl-tpy](2)(PF(6))(2), β(HRS) = 1040 × 10(-30) esu, ρ = 1.46) via structural motifs that possess intermediate values of the depolarization ratio. The chromophore design roadmap provided herein gives rise to octopolar supermolecules that feature by far the largest off-diagonal octopolar first hyperpolarizability tensor components ever reported, with the effectively octopolar Ru[4,4''-bis(Zn-porphyrin)ethynyl-tpy](2)(PF(6))(2) possessing a β(HRS) value at 1300 nm more than a factor of 3 larger than that determined for any chromophore having octopolar symmetry examined to date. Because NLO octopoles possess omnidirectional NLO responses while circumventing the electrostatic interactions that drive bulk-phase centrosymmetry for NLO dipoles at high chromophore concentrations, the advent of octopolar NLO chromophores having vastly superior β(HRS) values at technologically important wavelengths will motivate new experimental approaches to achieve acentric order in both bulk-phase and thin film structures.

Experimental Evidence of Dipolar Interaction in Bilayer Nanocomposite Magnets

DTIC Science & Technology

2010-11-25

corporated to improve experimental systems. However, re- ported bulk nanocomposite magnets exhibit (BH)max val- ues that are far below the...Appl Phys A DOI 10.1007/s00339-010-6073-6 Experimental evidence of dipolar interaction in bilayer nanocomposite magnets A.J. Zambano · H. Oguchi · I...Abstract We use magnetic thin film hard/non/soft-mag- netic trilayer systems to probe the nature of the hard–soft phase interaction and the role

Thermal entanglement and teleportation in a dipolar interacting system

NASA Astrophysics Data System (ADS)

Castro, C. S.; Duarte, O. S.; Pires, D. P.; Soares-Pinto, D. O.; Reis, M. S.

2016-04-01

Quantum teleportation, which depends on entangled states, is a fascinating subject and an important branch of quantum information processing. The present work reports the use of a dipolar spin thermal system as a noisy quantum channel to perform quantum teleportation. Non-locality, tested by violation of Bell's inequality and thermal entanglement, measured by negativity, shows that for the present model all entangled states, even those that do not violate Bell's inequality, are useful for teleportation.

Applying "domino" model to study dipolar geomagnetic field reversals and secular variation

NASA Astrophysics Data System (ADS)

Peqini, Klaudio; Duka, Bejo

2014-05-01

Aiming to understand the physical processes underneath the reversals events of geomagnetic field, different numerical models have been conceived. We considered the so named "domino" model, an Ising-Heisenberg model of interacting magnetic spins aligned along a ring [Mazaud and Laj, EPSL, 1989; Mori et al., arXiv:1110.5062v2, 2012]. We will present here some results which are slightly different from the already published results, and will give our interpretation on the differences. Following the empirical studies of the long series of the axial magnetic moment (dipolar moment or "magnetization") generated by the model varying all model parameters, we defined the set of parameters that supply the longest mean time between reversals. Using this set of parameters, a short time series (about 10,000 years) of axial magnetic moment was generated. After de-noising the fluctuation of this time series, we compared it with the series of dipolar magnetic moment values supplied by CALS10K.1b model for the last 10000 years. We found similar behavior of the both series, even if the "domino" model could not supply a full explanation of the geomagnetic field SV. In a similar way we will compare a 14000 years long series with the dipolar magnetic moment obtained by the model SHA.DIF.14k [Pavón-Carrasco et al., EPSL, 2014].

Reply to "Comment on 'Origin of tilted-phase generation in systems of ellipsoidal molecules with dipolar interactions' "

NASA Astrophysics Data System (ADS)

Bose, Tushar Kanti; Saha, Jayashree

2014-04-01

In a recent article [T. K. Bose and J. Saha, Phys. Rev. E 86, 050701 (2012), 10.1103/PhysRevE.86.050701], we have presented the results of a Monte Carlo simulation study of the systems of dipolar Gay-Berne ellipsoids where two terminal antiparallel dipoles are placed symmetrically on the long axis of each ellipsoid, and the results revealed the combined contribution of dipolar separation and transverse orientations in controlling the tilt angle in the tilted hexatic smectic phase. The tilt angle changed from zero to a significant value, in the case of transverse dipoles, with a change in the dipolar separation. In the related comment, Madhusudana [preceding Comment, Phys. Rev. E 89, 046501 (2014), 10.1103/PhysRevE.89.046501] has claimed that the physical origin of the molecular tilt in the significantly tilted phases found in the simulations is similar to that proposed by McMillan [Phys. Rev. A 8, 1921 (1973), 10.1103/PhysRevA.8.1921]. Here, we explain that the claim is not correct and make it clear that the two compared pictures are quite different. In the preceding Comment, Madhusudana has also suggested an alternative explanation for tilt generation in the simulations by criticizing the original one proposed by us. We argue here in support of the original explanation and clarify that his explanation does not follow the simulation results.

Observations and Simulations of Electron Dynamics Near an Active Neutral Line

NASA Technical Reports Server (NTRS)

Goldstein, M. L.; Hwang, Kyoung-Joo; Ashour-Abdalla, Maha; El-Aloui, Mostafa; Schriver, David; Richard, Robert; Zhou, Meng; Walker, Ray

2010-01-01

Recent observations in the Earth's magnetotail have shown rapid increases in the fluxes of energetic electrons with energies up to 100's of keV associated with dipolarization fronts that propagate into the inner magnetosphere. On August 15, 2001 the four Cluster spacecraft located slightly dawnward of midnight (yGSM approx. -5.4RE) at xGSM approx. -18RE observed a series of earthward propagating dipolarization fronts [Hwang et al., 2010]. At least 6 dipolarization fronts were observed in a 20m interval. Unlike previously reported cases the fluxes of electrons up to 95keV decreased during the passage of the first three fronts over the spacecraft. The energetic electron fluxes increased during the passage of the last three fronts. We have performed a global magnetohydrodynamic simulation of this event using solar wind observations from the ACE satellite to drive the simulation. In the simulation a very complex reconnection system in the near-Earth tail at XGSM approx. -20RE launched a series of earthward propagating dipolarization fronts that are similar to those observed on Cluster. The simulation results indicate that the Cluster spacecraft were just earthward of the reconnection site. In this paper we will present a study of the dynamics of electrons associated with these events by using the large-scale kinetic simulation approach in which we launch a large number of electrons into the electric and magnetic fields from this simulation.

Multiprobe Spectroscopic Inverstigation of Molecular-level Behavior within Aqueous 1-Butyl-3-methylimidazolium Tetrafluoroborate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sarkar, Abhra; Ali, Maroof; Baker, Gary A

2009-01-01

In this work, an array of molecular-level solvent featuressincluding solute-solvent/solvent-solvent interactions, dipolarity, heterogeneity, dynamics, probe accessibility, and diffusionswere investigated across the entire composition of ambient mixtures containing the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [bmim][BF4], and pH 7.0 phosphate buffer, based on results assembled for nine different molecular probes utilized in a range of spectroscopic modes. These studies uncovered interesting and unusual solvatochromic probe behavior within this benchmark mixture. Solvatochromic absorbance probessa watersoluble betaine dye (betaine dye 33), N,N-diethyl-4-nitroaniline, and 4-nitroanilineswere employed to determine ET (a blend of dipolarity/polarizability and hydrogen bond donor contributions) and the Kamlet-Taft indices * (dipolarity/polarizability), R (hydrogenmore » bond donor acidity), and (hydrogen bond acceptor basicity) characterizing the [bmim][BF4] + phosphate buffer system. These parameters each showed a marked deviation from ideality, suggesting selective solvation of the individual probe solutes by [bmim][BF4]. Similar conclusions were derived from the responses of the fluorescent polarity-sensitive probes pyrene and pyrene-1-carboxaldehyde. Importantly, the fluorescent microfluidity probe 1,3-bis(1-pyrenyl)propane senses a microviscosity within the mixture that significantly exceeds expectations derived from simple interpolation of the behavior in the neat solvents. On the basis of results from this probe, a correlation between microviscosity and bulk viscosity was established; pronounced solvent-solvent hydrogen-bonding interactions were implicit in this behavior. The greatest deviation from ideal additive behavior for the probes studied herein was consistently observed to occur in the buffer-rich regime. Nitromethane-based fluorescence quenching of pyrene within the [bmim][BF4] + phosphate buffer system showed unusual compliance with a sphere-of-action quenching model, a further manifestation of the microheterogeneity of the system. Fluorescence correlation spectroscopic results for both small (BODIPY FL) and macromolecular (Texas Red-10 kDa dextran conjugate) diffusional probes provide additional evidence in support of microphase segregation inherent to aqueous [bmim][BF4].« less

Micromagnetic simulations with periodic boundary conditions: Hard-soft nanocomposites

DOE PAGES

Wysocki, Aleksander L.; Antropov, Vladimir P.

2016-12-01

Here, we developed a micromagnetic method for modeling magnetic systems with periodic boundary conditions along an arbitrary number of dimensions. The main feature is an adaptation of the Ewald summation technique for evaluation of long-range dipolar interactions. The method was applied to investigate the hysteresis process in hard-soft magnetic nanocomposites with various geometries. The dependence of the results on different micromagnetic parameters was studied. We found that for layered structures with an out-of-plane hard phase easy axis the hysteretic properties are very sensitive to the strength of the interlayer exchange coupling, as long as the spontaneous magnetization for the hardmore » phase is significantly smaller than for the soft phase. The origin of this behavior was discussed. Additionally, we investigated the soft phase size optimizing the energy product of hard-soft nanocomposites.« less

Dynamic separation of nanomagnet sublattices by orientation of elliptical elements

NASA Astrophysics Data System (ADS)

Yahagi, Y.; Berk, C. R.; Harteneck, B. D.; Cabrini, S. D.; Schmidt, H.

2014-04-01

We report the separation of the magnetization dynamics of densely packed nanomagnets depending on their orientation. The arrays consist of interleaved sublattices of identical nickel elliptical disks. By controlling the orientation of the elliptic disks relative to the external field in each sublattice, we simultaneously analyzed the magnetization dynamics in each sublattice using a time-resolved magnetooptic Kerr effect (TR-MOKE) microscopy system. The Fourier spectra showed clearly separated precession modes for sublattices with different orientations. The spectra were shown to be robust against the error in applied field orientation. The sublattice response can be tuned to a single collective frequency by choosing a symmetric field orientation. We analyzed the effect of the interelement coupling with various spacing between nanomagnets and found a relatively weak dependence on dipolar interactions in good agreement with micromagnetic simulations.

Influence of solvent and salt concentration on the alignment properties of acrylamide copolymer gels for the measurement of RDC.

PubMed

Trigo-Mouriño, Pablo; Navarro-Vázquez, Armando; Sánchez-Pedregal, Víctor M

2012-12-01

The dependence of molecular alignment with solvent nature and salt concentration has been investigated for mechanically stretched polyacrylamide copolymer gels. Residual dipolar couplings (RDCs) were recorded for D(2)O, DMSO-d(6), and DMSO-d(6)/D(2)O solutions containing different proportions of the solvents and different sodium chloride concentrations. Alignment tensors were determined by fitting the experimental RDCs to the DFT-computed structure of N-methylcodeinium ion. Analysis of the tensors shows that the degree of alignment decreases with the proportion of DMSO-d(6) as well as with the concentration of sodium chloride, most likely due to enhanced ion-pair aggregation. Furthermore, rotation of the alignment tensor is observed when increasing the salt concentration. Copyright © 2012 John Wiley & Sons, Ltd.

Formation of reactive oxygen by N2O decomposition over binuclear cationic sites of Fe-ferrierite zeolite: Periodic DFT + U study

NASA Astrophysics Data System (ADS)

Avdeev, Vasilii I.; Bedilo, Alexander F.

2018-03-01

The electronic nature of sites over Fe-ferrierite zeolite stabilizing active α-oxygen is analyzed by the periodic DFT + U approach. It is shown that two antiferromagnetically coupled Fe2+ cations with bridging OH-bonds form a stable bi-nuclear site of the [Fe2+<2OH>Fe2+] doped FER complex. Frontier orbitals of this complex populated by two electrons with minority spins are localized in the bandgap. As a result, [Fe2+<2OH>Fe2+] unit acquires the properties of a binuclear Lewis acid dipolarophile for 1,3-dipole N2O. First reaction step of N2O decomposition follows the Huisgen‧s concept of the 1,3-dipolar cycloaddition concept followed by the formation of reactive oxygen species Fesbnd O.

Delta-opiate DPDPE in magnetically oriented phospholipid micelles: binding and arrangement of aromatic pharmacophores.

PubMed Central

Rinaldi, F; Lin, M; Shapiro, M J; Petersheim, M

1997-01-01

D-Penicillamine(2,5)-enkephalin (DPDPE) is a potent opioid peptide that exhibits a high selectivity for the delta-opiate receptors. This zwitterionic peptide has been shown, by pulsed-field gradient 1H NMR diffusion studies, to have significant affinity for a zwitterionic phospholipid bilayer. The bilayer lipid is in the form of micelles composed of dihexanoylphosphatidylcholine (DHPC) and dimyristoylphosphatidylcholine (DMPC) mixtures, where the DMPC forms the bilayer structure. At high lipid concentration (25% w/w) these micelles orient in the magnetic field of an NMR spectrometer. The resulting 1H-13C dipolar couplings and chemical shift changes in the natural abundance 13C resonances for the Tyr and Phe aromatic rings were used to characterize the orientations in the bilayer micelles of these two key pharmacophores. Images FIGURE 1 FIGURE 8 PMID:9414244

Exchange bias effect in L10-ordered FePt and FeCo-based bilayer structure: effect of increasing applied field

NASA Astrophysics Data System (ADS)

Singh, Sadhana; Kumar, Dileep; Bhagat, Babli; Choudhary, R. J.; Reddy, V. R.; Gupta, Ajay

2018-02-01

The applied magnetic field (H APP) dependence of the exchange bias (EB) is studied in an exchange-coupled thin-film bilayer composed of a hard ferromagnetic FePt layer in the proximity of a soft ferromagnetic FeCo layer. FePt/FeCo structure is deposited in an ultra-high vacuum chamber, where the FePt layer was first annealed at 823 K for 30 min and subsequently cooled to room temperature in the presence of an in-plane magnetic field, H MAX ~ 1.5 kOe to promote L10-ordered hard magnetic phase with magnetic moments aligned in one of the in-plane directions in the FePt layer. In-situ magneto-optical Kerr effect measurements during different stages of bilayer growth and detailed ex-situ superconducting quantum interference device-vibrating sample magnetometer measurements jointly revealed that due to the interplay between exchange coupling at the interface and dipolar energies of the saturated hard FePt layer, a hysteresis loop of FeCo layer shifts along the magnetic field axis. A clear dependence of EB field (H EB) on increasing maximum value of the H APP during the hysteresis loop measurement is understood in terms of the magnetic state of soft and hard magnetic layers, where EB increases with increasing H APP until the hard layer moment remains undisturbed in its remanence state. As soon as the field was sufficient to rotate the spins of the FePt layer, the loop became symmetric with respect to the field axis.

Temperature Dependence of the Thermal Conductivity of a Trapped Dipolar Bose-Condensed Gas

NASA Astrophysics Data System (ADS)

Yavari, H.

2018-02-01

The thermal conductivity of a trapped dipolar Bose condensed gas is calculated as a function of temperature in the framework of linear response theory. The contributions of the interactions between condensed and noncondensed atoms and between noncondensed atoms in the presence of both contact and dipole-dipole interactions are taken into account to the thermal relaxation time, by evaluating the self-energies of the system in the Beliaev approximation. We will show that above the Bose-Einstein condensation temperature ( T > T BEC ) in the absence of dipole-dipole interaction, the temperature dependence of the thermal conductivity reduces to that of an ideal Bose gas. In a trapped Bose-condensed gas for temperature interval k B T << n 0 g B , E p << k B T ( n 0 is the condensed density and g B is the strength of the contact interaction), the relaxation rates due to dipolar and contact interactions between condensed and noncondensed atoms change as {τ}_{dd12}^{-1}∝ {e}^{-E/{k}_BT} and τ c12 ∝ T -5, respectively, and the contact interaction plays the dominant role in the temperature dependence of the thermal conductivity, which leads to the T -3 behavior of the thermal conductivity. In the low-temperature limit, k B T << n 0 g B , E p >> k B T, since the relaxation rate {τ}_{c12}^{-1} is independent of temperature and the relaxation rate due to dipolar interaction goes to zero exponentially, the T 2 temperature behavior for the thermal conductivity comes from the thermal mean velocity of the particles. We will also show that in the high-temperature limit ( k B T > n 0 g B ) and low momenta, the relaxation rates {τ}_{c12}^{-1} and {τ}_{dd12}^{-1} change linearly with temperature for both dipolar and contact interactions and the thermal conductivity scales linearly with temperature.

DNA Nanotubes for NMR Structure Determination of Membrane Proteins

PubMed Central

Bellot, Gaëtan; McClintock, Mark A.; Chou, James J; Shih, William M.

2013-01-01

Structure determination of integral membrane proteins by solution NMR represents one of the most important challenges of structural biology. A Residual-Dipolar-Coupling-based refinement approach can be used to solve the structure of membrane proteins up to 40 kDa in size, however, a weak-alignment medium that is detergent-resistant is required. Previously, availability of media suitable for weak alignment of membrane proteins was severely limited. We describe here a protocol for robust, large-scale synthesis of detergent-resistant DNA nanotubes that can be assembled into dilute liquid crystals for application as weak-alignment media in solution NMR structure determination of membrane proteins in detergent micelles. The DNA nanotubes are heterodimers of 400nm-long six-helix bundles each self-assembled from a M13-based p7308 scaffold strand and >170 short oligonucleotide staple strands. Compatibility with proteins bearing considerable positive charge as well as modulation of molecular alignment, towards collection of linearly independent restraints, can be introduced by reducing the negative charge of DNA nanotubes via counter ions and small DNA binding molecules. This detergent-resistant liquid-crystal media offers a number of properties conducive for membrane protein alignment, including high-yield production, thermal stability, buffer compatibility, and structural programmability. Production of sufficient nanotubes for 4–5 NMR experiments can be completed in one week by a single individual. PMID:23518667

DNA nanotubes for NMR structure determination of membrane proteins.

PubMed

Bellot, Gaëtan; McClintock, Mark A; Chou, James J; Shih, William M

2013-04-01

Finding a way to determine the structures of integral membrane proteins using solution nuclear magnetic resonance (NMR) spectroscopy has proved to be challenging. A residual-dipolar-coupling-based refinement approach can be used to resolve the structure of membrane proteins up to 40 kDa in size, but to do this you need a weak-alignment medium that is detergent-resistant and it has thus far been difficult to obtain such a medium suitable for weak alignment of membrane proteins. We describe here a protocol for robust, large-scale synthesis of detergent-resistant DNA nanotubes that can be assembled into dilute liquid crystals for application as weak-alignment media in solution NMR structure determination of membrane proteins in detergent micelles. The DNA nanotubes are heterodimers of 400-nm-long six-helix bundles, each self-assembled from a M13-based p7308 scaffold strand and >170 short oligonucleotide staple strands. Compatibility with proteins bearing considerable positive charge as well as modulation of molecular alignment, toward collection of linearly independent restraints, can be introduced by reducing the negative charge of DNA nanotubes using counter ions and small DNA-binding molecules. This detergent-resistant liquid-crystal medium offers a number of properties conducive for membrane protein alignment, including high-yield production, thermal stability, buffer compatibility and structural programmability. Production of sufficient nanotubes for four or five NMR experiments can be completed in 1 week by a single individual.

Isoxazolodihydropyridinones: 1,3-dipolar cycloaddition of nitrile oxides onto 2,4-dioxopiperidines

PubMed Central

Coffman, Keith C.; Hartley, Timothy P.; Dallas, Jerry L.; Kurth, Mark J.

2012-01-01

Practical and efficient methods have been developed for the diversity-oriented synthesis of isoxazolodihydropyridinones via the 1,3-dipolar cycloaddition of nitrile oxides onto 2,4-dioxopiperidines. A select few of these isoxazolodihydropyridinones were further elaborated with triazoles by copper catalyzed azide-alkyne cycloaddition reactions. A total of 70 compounds and intermediates were synthesized and analyzed for drug likeness. Sixty-four of these novel compounds were submitted to the NIH Molecular Libraries Small Molecule Repository for high-throughput biological screening. PMID:22352295

Energy landscape in frustrated systems: Cation hopping in pyrochlores

NASA Astrophysics Data System (ADS)

Brooks Hinojosa, Beverly; Asthagiri, Aravind; Nino, Juan C.

2013-07-01

We investigate the dynamics of the local environment and electronic structure in inherently dipolar frustrated pyrochlore compounds to help identify the fundamental nature of dipolar disorder in pyrochlore systems and determine the necessary and sufficient conditions for dielectric relaxation. We map out the energy landscape associated with cation hopping events in three compounds and correlate the hopping pathway with experimental dielectric response. Comprehensive analysis of the calculations allows us to postulate rules to predict the occurrence of relaxation and cation hopping pathways.

Spreading dynamics of 2D dipolar Langmuir monolayer phases.

PubMed

Heinig, P; Wurlitzer, S; Fischer, Th M

2004-07-01

We study the spreading of a liquid 2D dipolar droplet in a Langmuir monolayer. Interfacial tensions (line tensions) and microscopic contact angles depend on the scale on which they are probed and obey a scaling law. Assuming rapid equilibration of the microscopic contact angle and ideal slippage of the 2D solid/liquid and solid/gas boundary, the driving force of spreading is merely expressed by the shape-dependent long-range interaction integrals. We obtain good agreement between experiment and numerical simulations using this theory.

A simple model of solvent-induced symmetry-breaking charge transfer in excited quadrupolar molecules

NASA Astrophysics Data System (ADS)

Ivanov, Anatoly I.; Dereka, Bogdan; Vauthey, Eric

2017-04-01

A simple model has been developed to describe the symmetry-breaking of the electronic distribution of AL-D-AR type molecules in the excited state, where D is an electron donor and AL and AR are identical acceptors. The origin of this process is usually associated with the interaction between the molecule and the solvent polarization that stabilizes an asymmetric and dipolar state, with a larger charge transfer on one side than on the other. An additional symmetry-breaking mechanism involving the direct Coulomb interaction of the charges on the acceptors is proposed. At the same time, the electronic coupling between the two degenerate states, which correspond to the transferred charge being localised either on AL or AR, favours a quadrupolar excited state with equal amount of charge-transfer on both sides. Because of these counteracting effects, symmetry breaking is only feasible when the electronic coupling remains below a threshold value, which depends on the solvation energy and the Coulomb repulsion energy between the charges located on AL and AR. This model allows reproducing the solvent polarity dependence of the symmetry-breaking reported recently using time-resolved infrared spectroscopy.

Solution NMR studies of Chlorella virus DNA ligase-adenylate.

PubMed

Piserchio, Andrea; Nair, Pravin A; Shuman, Stewart; Ghose, Ranajeet

2010-01-15

DNA ligases are essential guardians of genome integrity by virtue of their ability to recognize and seal 3'-OH/5'-phosphate nicks in duplex DNA. The substrate binding and three chemical steps of the ligation pathway are coupled to global and local changes in ligase structure, involving both massive protein domain movements and subtle remodeling of atomic contacts in the active site. Here we applied solution NMR spectroscopy to study the conformational dynamics of the Chlorella virus DNA ligase (ChVLig), a minimized eukaryal ATP-dependent ligase consisting of nucleotidyltransferase, OB, and latch domains. Our analysis of backbone (15)N spin relaxation and (15)N,(1)H residual dipolar couplings of the covalent ChVLig-AMP intermediate revealed conformational sampling on fast (picosecond to nanosecond) and slow timescales (microsecond to millisecond), indicative of interdomain and intradomain flexibility. We identified local and global changes in ChVLig-AMP structure and dynamics induced by phosphate. In particular, the chemical shift perturbations elicited by phosphate were clustered in the peptide motifs that comprise the active site. We hypothesize that phosphate anion mimics some of the conformational transitions that occur when ligase-adenylate interacts with the nick 5'-phosphate. Copyright 2009 Elsevier Ltd. All rights reserved.

Biosynthetically directed fractional 13C labeling facilitates identification of Phe and Tyr aromatic signals in proteins.

PubMed

Jacob, Jaison; Louis, John M; Nesheiwat, Issa; Torchia, Dennis A

2002-11-01

Analysis of 2D [(13)C,(1)H]-HSQC spectra of biosynthetic fractionally (13)C labeled proteins is a reliable, straightforward means to obtain stereospecific assignments of Val and Leu methyl sites in proteins. Herein we show that the same fractionally labeled protein sample facilitates observation and identification of Phe and Tyr aromatic signals. This is the case, in part, because the fractional (13)C labeling yields aromatic rings in which some of the (13)C-(13)C J-couplings, present in uniformly labeled samples, are absent. Also, the number of homonuclear J-coupling partners differs for the delta-, epsilon- and zeta-carbons. This enabled us to vary their signal intensities in distinctly different ways by appropriately setting the (13)C constant-time period in 2D [(13)C,(1)H]-HSQC spectra. We illustrate the application of this approach to an 18 kDa protein, c-VIAF, a modulator of apoptosis. In addition, we show that cancellation of the aromatic (13)C CSA and (13)C-(1)H dipolar interactions can be fruitfully utilized in the case of the fractionally labeled sample to obtain high resolution (13)C constant-time spectra with good sensitivity.

Transverse relaxation of scalar-coupled protons.

PubMed

Segawa, Takuya F; Baishya, Bikash; Bodenhausen, Geoffrey

2010-10-25

In a preliminary communication (B. Baishya, T. F. Segawa, G. Bodenhausen, J. Am. Chem. Soc. 2009, 131, 17538-17539), we recently demonstrated that it is possible to obtain clean echo decays of protons in biomolecules despite the presence of homonuclear scalar couplings. These unmodulated decays allow one to determine apparent transverse relaxation rates R(2) (app) of individual protons. Herein, we report the observation of R(2) (app) for three methyl protons, four amide H(N) protons, and all 11 backbone H(α) protons in cyclosporin A. If the proton resonances overlap, their R(2) (app) rates can be measured by transferring their magnetization to neighboring (13)C nuclei, which are less prone to overlap. The R(2) (app) rates of protons attached to (13)C are faster than those attached to (12)C because of (13)C-(1)H dipolar interactions. The differences of these rates allow the determination of local correlation functions. Backbone H(N) and H(α) protons that have fast decay rates R(2) (app) also feature fast longitudinal relaxation rates R(1) and intense NOESY cross peaks that are typical of crowded environments. Variations of R(2) (app) rates of backbone H(α) protons in similar amino acids reflect differences in local environments.

Low density mesostructures of confined dipolar particles in an external field

NASA Astrophysics Data System (ADS)

Richardi, J.; Weis, J.-J.

2011-09-01

Mesostructures formed by dipolar particles confined between two parallel walls and subjected to an external field are studied by Monte Carlo simulations. The main focus of the work is the structural behavior of the Stockmayer fluid in the low density regime. The dependence of cluster thickness and ordering is estimated as a function of density and wall separation, the two most influential parameters, for large dipole moments and high field strengths. The great sensitivity of the structure to details of the short-range part of the interactions is pointed out. In particular, the attractive part of the Lennard-Jones potential is shown to play a major role in driving chain aggregation. The effect of confinement, evaluated by comparison with results for a bulk system, is most pronounced for a short range hard sphere potential. No evidence is found for a novel "gel-like" phase recently uncovered in low density dipolar colloidal suspensions [A. K. Agarwal and A. Yethiraj, Phys. Rev. Lett. 102, 198301 (2009), 10.1103/PhysRevLett.102.198301].

Dipolarizing flux bundles in the cis-geosynchronous magnetosphere: relationship between electric fields and energetic particle injections

NASA Astrophysics Data System (ADS)

Liu, J.; Angelopoulos, V.; Zhang, X. J.; Turner, D. L.; Gabrielse, C.; Runov, A.; Funsten, H. O.; Spence, H. E.

2015-12-01

Dipolarizing flux bundles (DFBs) are small flux tubes (typically < 3 RE in XGSM and YGSM) in the nightside magnetosphere that have magnetic field more dipolar than the background field. Although DFBs are known to accelerate particles to create energetic particle injections, their acceleration mechanism and importance in generating injections inside geosynchronous orbit remain open questions. To answer these questions, we investigate DFBs in the inner magnetosphere by conducting a statistical study with data from the Van Allen Probes. The results show that just like DFBs outside geosynchronous orbit, those inside that orbit occur most often in the pre-midnight sector. Half the DFBs are accompanied by energetic particle injection. Statistically, DFBs with injection have an electric field three times that of those without. All the injections accompanying DFBs appear dispersionless within the temporal and energy resolution considered. These findings suggest that the injections are ushered or locally produced by the DFB, and the DFB's strong electric field is an important aspect of the injection generation mechanism.

Nanoscale control of competing interactions and geometrical frustration in a dipolar trident lattice.

PubMed

Farhan, Alan; Petersen, Charlotte F; Dhuey, Scott; Anghinolfi, Luca; Qin, Qi Hang; Saccone, Michael; Velten, Sven; Wuth, Clemens; Gliga, Sebastian; Mellado, Paula; Alava, Mikko J; Scholl, Andreas; van Dijken, Sebastiaan

2017-10-17

Geometrical frustration occurs when entities in a system, subject to given lattice constraints, are hindered to simultaneously minimize their local interactions. In magnetism, systems incorporating geometrical frustration are fascinating, as their behavior is not only hard to predict, but also leads to the emergence of exotic states of matter. Here, we provide a first look into an artificial frustrated system, the dipolar trident lattice, where the balance of competing interactions between nearest-neighbor magnetic moments can be directly controlled, thus allowing versatile tuning of geometrical frustration and manipulation of ground state configurations. Our findings not only provide the basis for future studies on the low-temperature physics of the dipolar trident lattice, but also demonstrate how this frustration-by-design concept can deliver magnetically frustrated metamaterials.Artificial magnetic nanostructures enable the study of competing frustrated interactions with more control over the system parameters than is possible in magnetic materials. Farhan et al. present a two-dimensional lattice geometry where the frustration can be controlled by tuning the unit cell parameters.

Designing Hysteresis with Dipolar Chains

NASA Astrophysics Data System (ADS)

Concha, Andrés; Aguayo, David; Mellado, Paula

2018-04-01

Materials that have hysteretic response to an external field are essential in modern information storage and processing technologies. A myriad of magnetization curves of several natural and artificial materials have previously been measured and each has found a particular mechanism that accounts for it. However, a phenomenological model that captures all the hysteresis loops and at the same time provides a simple way to design the magnetic response of a material while remaining minimal is missing. Here, we propose and experimentally demonstrate an elementary method to engineer hysteresis loops in metamaterials built out of dipolar chains. We show that by tuning the interactions of the system and its geometry we can shape the hysteresis loop which allows for the design of the softness of a magnetic material at will. Additionally, this mechanism allows for the control of the number of loops aimed to realize multiple-valued logic technologies. Our findings pave the way for the rational design of hysteretical responses in a variety of physical systems such as dipolar cold atoms, ferroelectrics, or artificial magnetic lattices, among others.

Energy limits of electron acceleration in the plasma sheet during substorms: A case study with the Magnetospheric Multiscale (MMS) mission

NASA Astrophysics Data System (ADS)

Turner, D. L.; Fennell, J. F.; Blake, J. B.; Clemmons, J. H.; Mauk, B. H.; Cohen, I. J.; Jaynes, A. N.; Craft, J. V.; Wilder, F. D.; Baker, D. N.; Reeves, G. D.; Gershman, D. J.; Avanov, L. A.; Dorelli, J. C.; Giles, B. L.; Pollock, C. J.; Schmid, D.; Nakamura, R.; Strangeway, R. J.; Russell, C. T.; Artemyev, A. V.; Runov, A.; Angelopoulos, V.; Spence, H. E.; Torbert, R. B.; Burch, J. L.

2016-08-01

We present multipoint observations of earthward moving dipolarization fronts and energetic particle injections from NASA's Magnetospheric Multiscale mission with a focus on electron acceleration. From a case study during a substorm on 02 August 2015, we find that electrons are only accelerated over a finite energy range, from a lower energy threshold at 7-9 keV up to an upper energy cutoff in the hundreds of keV range. At energies lower than the threshold energy, electron fluxes decrease, potentially due to precipitation by strong parallel electrostatic wavefields or initial sources in the lobes. Electrons at energies higher than the threshold are accelerated cumulatively by a series of impulsive magnetic dipolarization events. This case demonstrates how the upper energy cutoff increases, in this case from 130 keV to >500 keV, with each dipolarization/injection during sustained activity. We also present a simple model accounting for these energy limits that reveals that electron energization is dominated by betatron acceleration.

Designing Hysteresis with Dipolar Chains.

PubMed

Concha, Andrés; Aguayo, David; Mellado, Paula

2018-04-13

Materials that have hysteretic response to an external field are essential in modern information storage and processing technologies. A myriad of magnetization curves of several natural and artificial materials have previously been measured and each has found a particular mechanism that accounts for it. However, a phenomenological model that captures all the hysteresis loops and at the same time provides a simple way to design the magnetic response of a material while remaining minimal is missing. Here, we propose and experimentally demonstrate an elementary method to engineer hysteresis loops in metamaterials built out of dipolar chains. We show that by tuning the interactions of the system and its geometry we can shape the hysteresis loop which allows for the design of the softness of a magnetic material at will. Additionally, this mechanism allows for the control of the number of loops aimed to realize multiple-valued logic technologies. Our findings pave the way for the rational design of hysteretical responses in a variety of physical systems such as dipolar cold atoms, ferroelectrics, or artificial magnetic lattices, among others.

Theoretical studies to elucidate the influence of magnetic dipolar interactions occurring in the magnetic nanoparticle systems, for biomedical applications

NASA Astrophysics Data System (ADS)

Osaci, M.; Cacciola, M.

2016-02-01

In recent years, the study of magnetic nanoparticles has been intensively developed not only for their fundamental theoretical interest, but also for their many technological applications, especially biomedical applications, ranging from contrast agents for magnetic resonance imaging to the deterioration of cancer cells via hyperthermia treatment. The theoretical and experimental research has shown until now that the magnetic dipolar interactions between nanoparticles can have a significant influence on the magnetic behaviour of the system. But, this influence is not well understood. It is clear that the magnetic dipolar interaction intensity is correlated with the nanoparticle concentration, volume fraction and magnetic moment orientations. In this paper, we try to understand the influence of magnetic dipolar interactions on the behaviour of magnetic nanoparticle systems, for biomedical applications. For the model, we considered spherical nanoparticles with uniaxial anisotropy and lognormal distribution of the sizes. The model involves a simulation stage of the spatial distribution and orientation of the nanoparticles and their easy axes of magnetic anisotropy, and an evaluation stage of the Néel relaxation time. To assess the Néel relaxation time, we are going to discretise and adapt, to the local magnetic field, the Coffey analytical solution for the equation Fokker-Planck describing the dynamics of magnetic moments of nanoparticles in oblique external magnetic field. There are three fundamental aspects of interest in our studies on the magnetic nanoparticles: their spatial & orientational distributions, concentrations and sizes.