Fraction of boroxol rings in vitreous boron oxide from a first-principles analysis of Raman and NMR spectra

We determine the fraction f of B atoms belonging to boroxol rings in vitreous boron oxide through a first-principles analysis. After generating a model structure of vitreous B2O3 by first-principles molecular dynamics, we address a large set of properties, including the neutron structure factor, the neutron density of vibrational states, the infrared spectra, the Raman spectra, and the 11B NMR spectra, and find overall good agreement with corresponding experimental data. From the analysis of Raman and 11B NMR spectra, we yield consistently for both probes a fraction f of approximately 0.75. This result indicates that the structure of vitreous boron oxide is largely dominated by boroxol rings.     

Structure of B2O3 Glass at High Pressure: A 11B Solid-State NMR Study

We report spectroscopic evidence for the pressure-induced structural changes in B2O3 glass quenched from melts at pressures up to 6 GPa using solid-state NMR. While all borons are tri-coordinated at 1 atm, the fraction of tetra-coordinated boron increases with pressure, being about 5% and 27% in the B2O3 glass quenched from melts at 2 and 6 GPa, respectively. The fraction of boroxol ring species increases with pressure up to 2 GPa and apparently decreases with further compression up to 6 GPa. Two densification mechanisms are proposed to explain the variation of boron species with pressure.     

β─BaB2O4晶体生长母液结构的分子动力学模拟研究

采用分子动力学模拟方法，研究了β-BaB₂O₄晶体生长母液BaB₂O₄-Na₂O二元系熔体的结构，Na₂O摩尔浓度分别为12.5%，20%，25%，30%．模拟给出的不同组分比下的B-O径向分布函数表明，随着Na₂O浓度的增加，第一峰峰值更高，峰形更尖锐．在模拟产生的一系列瞬态构型基础上，采用键序参数方法，结合环链统计，研究了母液溶体的局部结构．结果表明 关键词：     

Spectroscopic evidence of polymorphism in vitreous B2O3

Brillouin and Raman spectroscopy were performed on B2O3 glass compressed to 57 GPa at 273 K. Upon compression the sound velocities increase smoothly and the boroxol ring Raman mode vanishes by 11 GPa. Upon decompression the sound velocities follow a different path and at 3 GPa a discontinuity of 3 km/s in V(p) and 2 km/s in V(s) returns the velocities to the values seen on compression. After the transition, the boroxol ring Raman mode reappears. A second pressure cycle produces the same behavior, suggesting the 3 GPa transition occurs between vitreous polymorphs with different boron coordination.     

氧化硼玻璃的11B变温核磁共振研究

本文应用变温核磁共振(NMR)技术研究了氧化硼(B₂O₃)玻璃从玻璃态至融熔态之间的结构变化。实验表明,T>430℃时,以硼氧组环为基本组成单元的玻璃态结构开始解体;600℃2O₃双棱锥体分子相互连接而成的链状结构。链结构在T>930℃时发生断裂,最终成为游离的B₂O₃分子。 关键词：     

Solid-state NMR study of bioactive binary borosilicate glasses

A series of binary borosilicate glasses prepared by the sol-gel method are shown to be bioactive. Tetraethyl orthosilicate (TEOS) and trimethylborate (TMB) in acidic medium are used to prepare xB₂O₃·(1−x)SiO₂ glass systems for x=0.045-0.167. The formation of a layer of apatite-like mineral on the glass surface becomes apparent after soaking in simulated body fluid for 48 h. We have measured the ¹¹B-¹¹B homonuclear second moments of the borosilicate glasses and inferred that no macroscopic phase separation occurred in our glasses. The ¹¹B chemical shift data also show that the formation of clustered boroxol rings is negligible in our glass system. Although the bioactivity of our borosilicate glasses is less than that of CaO-SiO₂ sol-gel glasses, these simple binary systems could be taken as reference glass systems for the search of new bioactive borosilicate glasses.     

The NMR response of boroxol rings: a density functional theory study

Cluster models of boron oxide glasses are studied computationally using density functional theory. It is shown that the isotropic chemical shielding of boron in boroxol rings is about 5 ppm less than for boron in non-ring BO3/2 units, and that the quadrupole coupling in ring sites is about 0.1 MHz larger than in non-ring sites, confirming assignments made in glasses and crystalline model compounds. The chemical shielding anisotropy of these sites is computed and shown to be in agreement with recent experimental measurements. Furthermore, it is shown that the reason for the different responses is not the co-planarity of BO3/2 groups bound in rings, but rather the contraction in the B-O-B bond angle from about 134 degrees in relaxed structures to 120 degrees as found in rings.     

B-MQMAS and Si–{B} Double-Resonance NMR Studies on the Structure of Binary B2O3–SiO2 Glasses

Glasses in the system x B₂O₃·(1−x)SiO₂ (0.2≤x≤1.0) were studied using ¹¹B multiple quantum magic angle spinning NMR spectroscopy (MQMAS), ²⁹Si–\{¹¹B\} rotational echo adiabatic passage double-resonance and ²⁹Si–\}¹¹B\{ CP heteronuclear correlation spectroscopy. The results can be quantitatively interpreted in terms of a phase separation of the borosilicate glasses into a virtually SiO₂-free B₂O₃ phase and a mixed borosilicate phase. While the MQMAS spectra allowed the site speciation and resolution of at least two different ¹¹B resonances, attributable to BO_3/2 units consumed in boroxol rings, BO_3/2 units connecting the boroxol rings and BO_3/2 units involved in B–O–Si linkages, the analysis of the double-resonance data further elucidated the structure of the mixed borosilicate phase. The results indicate that only a fraction of 0.48 mol B₂O₃ can be accommodated per mole SiO₂, building a mixed borosilicate network.     

NMR as a probe of the relaxation of the magnetization in magnetic molecules

We investigate the time autocorrelation of the molecular magnetization M(t) for three classes of magnetic molecules (antiferromagnetic rings, grids, and nanomagnets), in contact with the phonon heat bath. For all three classes, we find that the exponential decay of the fluctuations of M(t) is characterized by a single characteristic time tau(T,B) for not too high temperature T and field B. This is reflected in a nearly single-Lorentzian shape of the spectral density of the fluctuations. We show that such fluctuations are effectively probed by NMR, and that our theory explains the recent phenomenological observation by Baek et al. [Phys. Rev. B 70, 134434 (2004)] that the Larmor-frequency dependence of 1/T(1) data in a large number of AFM rings fits to a single-Lorentzian form.     

Tuning the continuum ground state energy of NO2- 2 by water molecules

Electron scattering on NO-2, NO-2 x (H2O), and NO-2 x (H2O)(2) was performed in two storage rings. We confirm the presence of earlier reported NO2-2 dianion resonances and show that they remain when water is attached. Importantly, hydration tunes the energy: each water molecule lowers the ground state energy by 0.8 +/- 0.3 eV relative to the monoanion. NO2-2 is observed to decay by two-electron emission, possibly in combination with fragmentation. NO(2-)2 x (H2O) mainly decays into NO-2 + H2O + e(-).     

Structural and Interaction Properties of Porphyrin Layers — A Quantum Chemical Study

This paper is proposed to understand the interaction of porphyrin layers with diatomic molecules interacting at their interior regions by applying ab initio and density functional theory(DFT) methods. We have used NO, CO, and O2 diatomic molecules to interact with the porphyrin layers. The most common Fe-centered metalloporphyrin structure with tetra-pyrrlic rings having N4 core is chosen for the study. The optimization of Porphyrin-Porphyrin(P I-P II)and Porphyrin-Diatomic molecule-Porphyrin(P I-AB-P II)(AB = NO, CO, and O2) complexes are performed using HF method. In order to understand the planarity and appropriate stacking size of porphyrins and also to infer the separation of diatomic molecules between porphyrin layers the behavior of P I-AB-P II complexes(where AB = NO, CO, and O2)are analyzed using structural properties and molecular electrostatic potentials(MEP). The MEPs are calculated using hybrid exchange correlation functional B3PW91 of DFT along with 6-31+G* basis set for the P I-P II and P I-AB-P II complexes obtained from HF method.     

Phase fluctuations and the pseudogap in YBa(2)Cu(3)O (x)

The thermodynamics of the superconducting transition is studied as a function of doping using high-resolution expansivity data of YBa(2)Cu(3)O (x) single crystals and Monte Carlo simulations of the anisotropic 3D- XY model. We directly show that T(c) of underdoped YBa(2)Cu(3)O (x) is strongly suppressed from its mean-field value (T(MF)(c)) by phase fluctuations of the superconducting order parameter. For overdoped YBa(2)Cu(3)O (x) fluctuation effects are greatly reduced and T(c) approximately T(MF)(c). We find that T(MF)(c) exhibits a similar doping dependence as the pseudogap energy, naturally suggesting that the pseudogap arises from phase-incoherent Cooper pairing.     

Absence of intrinsic ferromagnetic interactions of isolated and paired Co dopant atoms in Zn1-xCoxO with high structural perfection

We report element specific structural and magnetic investigations on Zn(1-x)Co(x)O epitaxial films using synchrotron radiation. Co dopants exclusively occupy Zn sites as revealed by x-ray linear dichroism having an unprecedented degree of structural perfection. Comparative magnetic field dependent measurements by x-ray magnetic circular dichroism and conventional magnetometry consistently show purely paramagnetic behavior for isolated Co dopant atoms with a magnetic moment of 4.8 (mu B). However, the total magnetization is reduced by approximately 30%, demonstrating that Co-O-Co pairs are antiferromagnetically coupled. We find no sign of intrinsic ferromagnetic interactions for isolated or paired Co dopant atoms in Co:ZnO films.     

Spin conductance in three-terminal rings subject to Rashba and Dresselhaus spin-orbit coupling

Based on the Green's function formalism, we investigated spin transport properties in one-dimensional three-terminal rings in the presence of the Rashba spin-orbit coupling (RSOC) and Dresselhaus spin-orbit coupling (DSOC). The conductance as a function of the Fermi energy shows typical resonance and antiresonance (conductance zero) characteristics in the absence of spin-orbit coupling (SOC). When one type of SOC (RSOC or DSOC) is introduced, the original conductance zeros are lifted, but new conductance zeros emerge. It is found that all the conductance zeros depend sensitively on the disorder, and the fluctuate weakens and smoothens the oscillations of the conductance. In the presence of both types of SOCs, the interplay between the RSOC and the DSOC opens a gap in the energy spectrum and breaks the cylindrical symmetry of the ring. Consequently, symmetrically coupled three-terminal rings show anisotropic conductances, which are robust against weak disorders.     

B(0)-B(0) mixing in unquenched lattice QCD

We present an unquenched lattice calculation for the B(0)-B(0) transition amplitude. The calculation, carried out at an inverse lattice spacing 1/a=2.22(4) GeV, incorporates two flavors of dynamical quarks described by the O(a)-improved Wilson fermion action and heavy quarks described by nonrelativistic QCD. Particular attention is paid to the uncertainty that arises from the chiral extrapolation, especially the effect of pion loops, for light quarks, which we find could be sizable for the leptonic decay constant, whereas it is small for the B parameters. We obtain f(B(d))=191(10)(+12-22) MeV, f(B(s))/f(B(d))=1.13(3)(+13-2), B(B(d))(m(b))=0.836(27)(+56-62), B(B(s))/B(B(d))=1.017(16)(+56-17), and xi=1.14(3)(+13-2), where the first error is statistical, and the second is systematic, including uncertainties due to chiral extrapolation, finite lattice spacing, heavy quark expansion, and perturbative operator matching.     

Direct observation of the oxygen isotope effect on the in-plane magnetic field penetration depth in optimally doped YBa2Cu3O7-delta

We report the first direct observation of the oxygen-isotope ((16)O/(18)O) effect on the in-plane penetration depth lambda(ab) in a nearly optimally doped YBa(2)Cu(3)O(7-delta) film using the novel low-energy muon-spin rotation technique. Spin-polarized low-energy muons are implanted in the film at a known depth z beneath the surface and process in the local magnetic field B(z). This feature allows us to measure directly the profile B(z) of the magnetic field inside the superconducting film in the Meissner state and to make a straightforward determination of lambda(ab). A substantial isotope shift Delta lambda(ab)/lambda(ab)=2.8(1.0)% at 4 K is observed, implying that the in-plane effective supercarrier mass m*(ab) is oxygen-isotope dependent with Delta m*(ab)/m*(ab)=5.5(2.0)%. These results are in good agreement with magnetization measurements on powder samples.     

Metastable ringlike semitopological solitons

We show the existence of new stable ringlike localized scalar field configurations whose stability is due to a combination of topological and nontopological charges. In that sense these defects may be called semitopological. These rings are Noether charged and also carry Noether current (they are superconducting). They are local minima of the energy in scalar field theories with an unbroken U(1) global symmetry. We obtain numerical solutions of the field configuration corresponding to large rings and derive virial theorems demonstrating their stability. We also derive the minimum energy field configurations in 3D and simulate the evolution of a finite size Q ring on a three dimensional lattice.     

Direct observation of switching processes in permalloy rings with lorentz microscopy

To achieve a deeper understanding of the switching process of magnetic Permalloy rings, Lorentz electron microscopy (LTEM) is used for the first time to image the magnetic configuration of such rings under applied external field conditions. Because of the exceptionally high lateral resolution we find two clearly distiguishable wall configurations present in the so-called "onion state." Furthermore, we show that a bias field present during a remagnetization cycle prevents the rings from transforming into a flux closure state, in which case remagnetization is a pure domain wall motion process.     

Microwave-assisted switching of microscopic rings: correlation between nonlinear spin dynamics and critical microwave fields

We have studied the spin dynamics of microscopic permalloy rings at GHz frequencies. Increasing the irradiation power, we observe first nonlinear spin dynamics and second microwave-assisted switching (MAS). We explore the MAS phase diagram as a function of microwave power and frequency f and, in particular, extract the critical microwave field hc(f). Its frequency dependence reflects characteristic eigenfrequencies from both the linear and nonlinear spin-wave spectrum. By comparing hc(f) with the different susceptibilities, we gain insight into the microscopic processes which might be the basis of a predictive theory of MAS.     

B-meson decay constant from unquenched lattice QCD

We present determinations of the -meson decay constant f(B) and f(B)(s)/f(B) using the MILC Collaboration unquenched gauge configurations, which include three flavors of light sea quarks. The mass of one of the sea quarks is kept around the strange quark mass, and we explore a range in masses for the two lighter sea quarks down to m(s)/8. The heavy quark is simulated using nonrelativistic QCD, and both the valence and sea light quarks are represented by the highly improved (AsqTad) staggered quark action. The good chiral properties of the latter action allow for a more accurate chiral extrapolation to physical up and down quarks than has been possible in the past. We find f(B)=216(9)(19)(4)(6) MeV and f(B)(s)/f(B)=1.20(3)(1).