Strong Relaxation Research Articles

Detecting O2 binding sites in protein cavities.

Internal cavities are important elements in protein structure, dynamics, stability and function. Here we use NMR spectroscopy to investigate the binding of molecular oxygen (O2) to cavities in a well-studied model for ligand binding, the L99A mutant of T4 lysozyme. On increasing the O2 concentration to 8.9 mM, changes in 1H, 15N, and 13C chemical shifts and signal broadening were observed specifically for backbone amide and side chain methyl groups located around the two hydrophobic cavities of the protein. O2-induced longitudinal relaxation enhancements for amide and methyl protons could be adequately accounted for by paramagnetic dipolar relaxation. These data provide the first experimental demonstration that O2 binds specifically to the hydrophobic, and not the hydrophilic cavities, in a protein. Molecular dynamics simulations visualized the rotational and translational motions of O2 in the cavities, as well as the binding and egress of O2, suggesting that the channel consisting of helices D, E, G, H, and J could be the potential gateway for ligand binding to the protein. Due to strong paramagnetic relaxation effects, O2 gas-pressure NMR measurements can detect hydrophobic cavities when populated to as little as 1%, and thereby provide a general and highly sensitive method for detecting oxygen binding in proteins.

Understanding the optical properties of ZnO1−xSx and ZnO1−xSex alloys

ZnO1−xYx with chalcogen element Y exhibits intriguing optoelectronic properties as the alloying strongly impacts the band-gap energy Eg(x). In this work, we analyze and compare the electronic structures and the dielectric responses of Zn(O,S) and Zn(O,Se) alloys by means of the density functional theory and the partially self-consistent GW approach. We model the crystalline stability from the total energies, and the results indicate that Zn(O,S) is more stable as alloy than Zn(O,Se). We demonstrate also that ion relaxation strongly affects total energies, and that the band-gap bowing depends primarily on local relaxation of the bonds. Moreover, we show that the composition dependent band-gap needs to be analyzed by the band anti-crossing model for small alloying concentration, while the alloying band-bowing model is accurate for strong alloying. We find that the Se-based alloys have a stronger change in the band-gap energy (for instance, ΔEg(0.50) = Eg(ZnO) – Eg(x = 0.50) ≈ 2.2 eV) compared with that of the S-based alloy (ΔEg(0.50) = 1.2 eV), mainly due to a stronger relaxation of the Zn–anion bonds that affects the electronic structure near the band edges. The optical properties of the alloys are discussed in terms of the complex dielectric function ε(ω) = ε1(ω) + iε2(ω) and the absorption coefficient α(ω). While the large band-gap bowing directly impacts the low-energy absorption spectra, the high-frequency dielectric constant ε∞ is correlated to the intensity of the dielectric response at energies above 4 eV. Therefore, the dielectric constant is only weakly affected by the non-linear band-gap variation. Despite strong structural relaxation, the high absorption coefficients of the alloys demonstrate that the alloys have well-behaved optoelectronic properties.

Global optimization of non-convex generalized disjunctive programs: a review on reformulations and relaxation techniques

In this paper we present a review on the latest advances in logic-based solution methods for the global optimization of non-convex generalized disjunctive programs. Considering that the performance of these methods relies on the quality of the relaxations that can be generated, our focus is on the discussion of a general framework to find strong relaxations. We identify two main sources of non-convexities that any methodology to find relaxations should account for. Namely, the one arising from the non-convex functions and the one arising from the disjunctive set. We review the work that has been done on these two fronts with special emphasis on the latter. We then describe different logic-based optimization techniques that make use of the relaxation framework and its impact through a set of numerical examples typically encountered in Process Systems Engineering. Finally, we outline challenges and future lines of work in this area.

Site preference and lattice relaxation around 4d and 5d refractory elements in Ni3Al.

X-ray absorption spectroscopy is employed to investigate site preference and lattice relaxation around Mo, Ru, Hf, W and Re dopants in Ni3Al. The site occupation preference and the measured distances between the refractory elements as dopants and the nearest host atoms are compared with the results of ab initio calculations within the density functional theory. Combined experimental and theoretical results indicate that Mo, Hf, W and Re atoms reside on the Al sublattice in Ni3Al, while Ru atoms occupy the Ni sublattice. A more pronounced lattice relaxation was detected in the case of Hf and Ru doping, with a strong outward relaxation of the nearest Ni and Al atoms.

Relaxing Nonconvex Quadratic Functions by Multiple Adaptive Diagonal Perturbations

The current bottleneck of globally solving mixed-integer (non-convex) quadratically constrained problem (MIQCP) is still to construct strong but computationally cheap convex relaxations, especially when dense quadratic functions are present. We propose a cutting surface procedure based on multiple diagonal perturbations to derive strong convex quadratic relaxations for nonconvex quadratic problem with separable constraints. Our resulting relaxation does not use significantly more variables than the original problem, in contrast to many other relaxations based on lifting. The corresponding separation problem is a highly structured semidefinite program (SDP) with convex but non-smooth objective. We propose to solve this separation problem with a specialized primal-barrier coordinate minimization algorithm. Computational results show that our approach is very promising. First, our separation algorithm is at least an order of magnitude faster than interior point methods for SDPs on problems up to a few hundred variables. Secondly, on nonconvex quadratic integer problems, our cutting surface procedure provides lower bounds of almost the same strength with the diagonal SDP bounds used by (Buchheim and Wiegele, 2013) in their branch-and-bound code Q-MIST, while our procedure is at least an order of magnitude faster on problems with dimension greater than 70. Finally, combined with (linear) projected RLT cutting planes proposed by (Saxena, Bonami and Lee, 2011), our procedure provides slightly weaker bounds than their projected SDP+RLT cutting surface procedure, but in several order of magnitude shorter time. Finally we discuss various avenues to extend our work to design more efficient branch-and-bound algorithms for MIQCPs.

A unusual two-dimensional azido-Cu(ii) network with benzoate derivative as a co-ligand exhibiting ferromagnetic order and slow magnetic relaxation

A 2D layer-like Cu(ii) compound with multiple-bridges of azido, carboxylate and hydroxyl ligands, featuring strong ferromagnetic coupling and slow magnetic relaxation.

Electrical, Luminescent and Structural Properties of Nanopillar GaN/InGaN Multi-Quantum-Well Structures Prepared by Dry Etching

GaN/InGaN multiple quantum well (MQW) structures with undoped n-GaN cap imitating true light emitting diodes were grown on sapphire and converted to deep nanopillar (NP) structures by dry etching beyond the MQW region. Structural measurements, electrical measurements on Schottky diodes, microcathodoluminescence (MCL) spectra measurements indicate a strong relaxation of strain in NP MQWs manifested in the prominent increase of the bowing radius of the structures and in the blueshift of the MQW peak in MCL spectra. Various treatments of the as-etched NP MQWs (annealing at 700°C, etching in KOH, and soaking in (NH4)2S) progressively decreased the leakage current of Schottky diodes and increased the MQW MCL peak intensity due to the suppression of the dry-etching damage of the nanopillar sidewalls.

Advanced FeTiNbO6/poly(vinylidene fluoride) composites with a high dielectric permittivity near the percolation threshold

FeTiNbO6 (denoted as FTN) is a recently discovered giant dielectric material with high Curie temperature (550 K). In this work, well dispersive FTN particles with mean particle size about 500 nm were synthesized by the improved solid-state reaction method. Using FTN particles as fillers and poly(vinylidene fluoride) (denoted as PVDF) polymer as matrix, multi-volume ratio (0%–60%) homogeneous ceramic/polymer composites have been prepared through a hot-pressing technology. At the same filling content, the FTN/PVDF composites display higher dielectric permittivity compared to the normal reported BaTiO3/PVDF composites, even larger than that of PVDF based composites using giant dielectric CaCu3Ti4O12 as filler. Especially, for 40 vol. % FTN/PVDF composites, the dielectric permittivity is as high as 181 measured at 100 Hz and 25 °C. Through the theoretical analysis correlated with structure evolution observation, it is deduced that the high dielectric performance originates from the combined effect of a variety of factors, such as giant dielectric semiconducting FTN particles, the micro-capacitor structure, and percolation phenomenon at appropriate volume fraction of FTN. Moreover, FTN/PVDF composites present strong dielectric relaxation behavior, which results from the superposition of the dielectric relaxation between PVDF and FTN. These flexible, easy processing FTN/PVDF composites with large dielectric permittivity values could find applications as new generational embedded capacitors.

Manganese spin dephasing mechanisms in ferromagnetic (Ga,Mn)As

We report on the study of Mn transversal spin relaxation mechanisms in ferromagnetic (Ga,Mn)As. The spins of valence band holes experience exchange interactions with ferromagnetically ordered Mn spins and strong spin relaxation due to spin-orbit coupling. The hole subsystem provides a relaxation channel for the Mn spin subsystem. The Mn spin relaxation mechanisms were studied by means of spin flip Raman scattering. Two contributions to the spin flip Raman linewidth were found. The first one dominates below the Curie temperature and is related to the fast hole spin relaxation that damps the collective motion of the coupled Mn and hole spin subsystems. The other contribution to the Mn spin relaxation is related to spin fluctuations of the hole ensemble, which grow with temperature and become most important in the paramagnetic phase.

Structure of the solution set for a partial differential inclusion

In this paper, we consider the biharmonic problem of a partial differential inclusion with Dirichlet boundary conditions. We prove existence theorems for related partial differential inclusions with convex and nonconvex multivalued perturbations, and obtain an existence theorem on extremal solutions, and a strong relaxation theorem. Also we prove that the solution set is compact $R_{\delta}$ if the perturbation term of the related partial differential inclusion is convex, and its solution set is path-connected if the perturbation term is nonconvex.

Bin packing and related problems: General arc-flow formulation with graph compression

We present an exact method, based on an arc-flow formulation with side constraints, for solving bin packing and cutting stock problems—including multi-constraint variants—by simply representing all the patterns in a very compact graph. Our method includes a graph compression algorithm that usually reduces the size of the underlying graph substantially without weakening the model.Our formulation is equivalent to Gilmore and Gomory׳s, thus providing a very strong linear relaxation. However, instead of using column-generation in an iterative process, the method constructs a graph, where paths from the source to the target node represent every valid packing pattern.The same method, without any problem-specific parameterization, was used to solve a large variety of instances from several different cutting and packing problems. In this paper, we deal with vector packing, bin packing, cutting stock, cardinality constrained bin packing, cutting stock with cutting knife limitation, bin packing with conflicts, and other problems. We report computational results obtained with many benchmark test datasets, some of them showing a large advantage of this formulation with respect to the traditional ones.

Strong SOCP Relaxations for the Optimal Power Flow Problem

This paper proposes three strong second order cone programming (SOCP) relaxations for the AC optimal power flow (OPF) problem. These three relaxations are incomparable to each other and two of them are incomparable to the standard SDP relaxation of OPF. Extensive computational experiments show that these relaxations have numerous advantages over existing convex relaxations in the literature: (i) their solution quality is extremely close to that of the standard SDP relaxation (the best one is within 99.96% of the SDP relaxation on average for all the IEEE test cases) and consistently outperforms previously proposed convex quadratic relaxations of the OPF problem, (ii) the solutions from the strong SOCP relaxations can be directly used as a warm start in a local solver such as IPOPT to obtain a high quality feasible OPF solution, and (iii) in terms of computation times, the strong SOCP relaxations can be solved an order of magnitude faster than the standard SDP relaxation. For example, one of the proposed SOCP relaxations together with IPOPT produces a feasible solution for the largest instance in the IEEE test cases (the 3375-bus system) and also certifies that this solution is within 0.13% of global optimality, all this computed within 157.20 seconds on a modest personal computer. Overall, the proposed strong SOCP relaxations provide a practical approach to obtain feasible OPF solutions with extremely good quality within a time framework that is compatible with the real-time operation in the current industry practice.

Dielectric Properties in TbFeO3 Ceramics

Polycrystalline sample of TbFeO3 has been made by the traditional solid state reaction method. The sample exhibits single phase orthorhombic structure with space group Pbnm. The temperature dependences of the dielectric constant and loss tangent at different frequencies have been investigated in detail. Two strong relaxations have been observed in the investigated frequency range. The high- and low-temperature relaxations with activation energies of 0.31 and 0.32 eV may be ascribed to oxygen vacancy and the electrons hopping between Fe2+ and Fe3+ ions, respectively.

Hybrid Methods in Solving Alternating-Current Optimal Power Flows

Many steady-state problems in power systems, including rectangular power-voltage formulations of optimal power flows in the alternating-current model (ACOPF), can be cast as polynomial optimisation problems (POP). For a POP, one can derive strong convex relaxations, or rather hierarchies of ever stronger, but ever larger relaxations. We study means of switching from solving the convex relaxation to Newton method working on a non-convex Lagrangian of the POP.

Dynamic characterization of crystalline and glass phases of deuterated 1,1,2,2 tetrachloroethane.

A thorough characterization of the γ, β, and glass phases of deuterated 1,1,2,2 tetrachloroethane (C2D2Cl4) via nuclear quadrupole resonance and Molecular Dynamic Simulations (MDSs) is reported. The presence of molecular reorientations was experimentally observed in the glass phase and in the β phase. In the β phase, and from MDS, these reorientations are attributed to two possible movements, i.e., a 180° reorientation around the C2 molecular symmetry axis and a reorientation of the molecule between two non-equivalent positions. In the glass phase, the spin-lattice relaxation time T1 is of the order of 16 times lower than in the crystalline phase and varies as T(-1) below 100 K in good agreement with the strong quadrupolar relaxation observed in amorphous materials and in the glassy state of molecular organic systems. The activation energy of molecular reorientations in the glass phase (19 kJ/mol) is comparable to that observed in the glassy crystal of a "molecular cousin" compound, Freon 112 (C2F2Cl4), for the secondary β-relaxation. Moreover, the on-site orientational motion of tetrachloroethane molecules offers a new indirect evidence of the prominent role of such orientational disorder in glassy dynamics.

Secondary relaxation dynamics in rigid glass-forming molecular liquids with related structures.

The dielectric relaxation in three glass-forming molecular liquids, 1-methylindole (1MID), 5H-5-Methyl-6,7-dihydrocyclopentapyrazine (MDCP), and Quinaldine (QN) is studied focusing on the secondary relaxation and its relation to the structural α-relaxation. All three glass-formers are rigid and more or less planar molecules with related chemical structures but have dipoles of different strengths at different locations. A strong and fast secondary relaxation is detected in the dielectric spectra of 1MID, while no resolved β-relaxation is observed in MDCP and QN. If the observed secondary relaxation in 1MID is identified with the Johari-Goldstein (JG) β-relaxation, then apparently the relation between the α- and β-relaxation frequencies of 1MID is not in accord with the Coupling Model (CM). The possibility of the violation of the prediction in 1MID as due to either the formation of hydrogen-bond induced clusters or the involvement of intramolecular degree of freedom is ruled out. The violation is explained by the secondary relaxation originating from the in-plane rotation of the dipole located on the plane of the rigid molecule, contributing to dielectric loss at higher frequencies and more intense than the JG β-relaxation generated by the out-of-plane rotation. MDCP has smaller dipole moment located in the plane of the molecule; however, presence of the change of curvature of dielectric loss, ε″(f), at some frequency on the high-frequency flank of the α-relaxation reveals the JG β-relaxation in MDCP and which is in accord with the CM prediction. QN has as large an in-plane dipole moment as 1MID, and the absence of the resolved secondary relaxation is explained by the smaller coupling parameter than the latter in the framework of the CM.

β-detected NMR spin relaxation in a thin film heterostructure of ferromagnetic EuO

We present $\ensuremath{\beta}$-detected NMR measurements of the spin-lattice relaxation of $^{8}\mathrm{Li}^{+}$ implanted into an epitaxial heterostructure based on a 100 nm thick film of ferromagnetic (FM) EuO as a function of temperature through its FM transition. In the FM state, the spin-lattice relaxation rate follows the same temperature dependence, determined by magnon scattering mechanisms, observed in the bulk by $^{153}\mathrm{Eu}$ NMR, but above 40 K, the signal is wiped out. We also find that $^{8}\mathrm{Li}^{+}$ stopped in material adjacent to the magnetic layer exhibits spin relaxation related to the critical slowing of the Eu spins. A particularly strong relaxation in the Au overlayer suggests an unusual strong nonlocal coupling mechanism to $^{8}\mathrm{Li}$ in the metal.

Order-disorder type critical behavior at the magnetoelectric phase transition in multiferroicDyMnO3

We present the results of detailed dielectric investigations of the relaxation dynamics in ${\mathrm{DyMnO}}_{3}$ multiferroic manganite. A strong low-frequency relaxation process near the paraelectric-ferroelectric phase transition is observed. We provide experimental evidence to show that this relaxation mode corresponds to a chirality switching of the spin cycloid in ${\mathrm{DyMnO}}_{3}$. We demonstrate that the relaxation dynamics in ${\mathrm{DyMnO}}_{3}$ is typical for an order-disorder phase transition and may be understood within a simple model with a double-well potential. These results suggest the interpretation of the paraelectric sinusoidal phase in manganites as a dynamical equilibrium of magnetic cycloids with opposite chiralities.

Spin relaxation via exchange with donor impurity-bound electrons

At low temperatures, electrons in semiconductors are bound to shallow donor impurity ions, neutralizing their charge in equilibrium. Inelastic scattering of other externally-injected conduction electrons accelerated by electric fields can excite transitions within the manifold of these localized states. Promotion of the bound electron into highly spin-orbit-mixed excited states drives a strong spin relaxation of the conduction electrons via exchange interactions, reminiscent of the Bir-Aronov-Pikus process where exchange occurs with valence band hole states. Through low-temperature experiments with silicon spin transport devices and complementary theory, we reveal the consequences of this previously unknown spin depolarization mechanism both below and above the impact ionization threshold.

Direct Bandgap Group IV Epitaxy on Si for Laser Applications

The recent observation of a fundamental direct bandgap for GeSn group IV alloys and the demonstration of low temperature lasing provide new perspectives on the fabrication of Si photonic circuits. This work addresses the progress in GeSn alloy epitaxy aiming at room temperature GeSn lasing. Chemical vapor deposition of direct bandgap GeSn alloys with a high Γ- to L-valley energy separation and large thicknesses for efficient optical mode confinement is presented and discussed. Up to 1 μm thick GeSn layers with Sn contents up to 14 at. % were grown on thick relaxed Ge buffers, using Ge2H6 and SnCl4 precursors. Strong strain relaxation (up to 81%) at 12.5 at. % Sn concentration, translating into an increased separation between Γ- and L-valleys of about 60 meV, have been obtained without crystalline structure degradation, as revealed by Rutherford backscattering spectroscopy/ion channeling and transmission electron microscopy. Room temperature reflectance and photoluminescence measurements were performed to ...