Material Synthesis and Characterization on Low-Dimensional Cobaltates

In this thesis, results of the investigation of a new low-dimensional cobaltates Ba2-xSrxCoO 4 are presented. The synthesis of both polycrystalline and single crystalline compounds using the methods of conventional solid state chemical reaction and floating-zone optical furnace is first introduced. Besides making polycrystalline powders, we successfully, for the first time, synthesized large single crystals of Ba2CoO4. Single crystals were also obtained for Sr doped Ba2-xSrxCoO 4. Powder and single crystal x-ray diffraction results indicate that pure Ba2CoO4 has a monoclinic structure at room temperature. With Sr doping, the lattice structure changes to orthorhombic when x ≥ 0.5 and to tetragonal when x = 2.0. In addition, Ba2CoO4 and Sr2CoO4, have completely different basic building blocks in the structure. One is CoO4 tetrahedron and the later is CoO6 octahedron, respectively. Electronic and magnetic properties were characterized and discussed. The magnetic susceptibility, specific heat and thermal conductivity show that Ba2CoO4 has an antiferromagnetic (AF) ground state with an AF ordering temperature TN = 25 K. However, the magnitude of the Néel temperature TN is significantly lower than the Curie-Weiss temperature (:&thetas;: ∼ 110 K), suggesting either reduced-dimensional magnetic interactions and/or the existence of magnetic frustration. The AF interaction persists in all the samples with different doping concentrations. The Néel temperature doesn't vary much in the monoclinic structure regime but decreases when the system enters orthorhombic. Magnetically, Ba2CoO4 has an AF insulating ground state while Sr2CoO4 has a ferromagnetic (FM) metallic ground state. Neutron powder refinement results indicate a magnetic structure with the spin mostly aligned along the a-axis. The result from a μ-spin rotation/relaxation (μ+SR) experiment agrees with our refinement. It confirms the AF order in the ab -plane. We also studied the spin dynamics and its anisotropy in the AF phase. The results from inelastic neutron scattering show that spin waves have a clear dispersion along a-axis but not along c-axis, indicating spin anisotropy. This work finds the strong spin-lattice coupling in this novel complex material. The interplay between the two degrees of freedom results an interesting phase diagram. Further research is needed when large single crystal samples are available.

Anisotropia magnética em nanofilmes com assimetria cristalográfica

This Thesis comprises a theoretical study about the influence of the magnetocrystalline anisotropy on the static and dynamic magnetic properties of nanofilms: monolayers and trilayers coupled through the bilinear and biquadratic exchange fields, for situations in which the systems are grown in unusual [hkl] asymmetric directions. Using a theory based on a realistic phenomenological model for description of nanometric systems, we consider the total free magnetic energy including the Zeeman interaction, cubic and uniaxial anisotropies, demagnetizing and surface anysotropy energies, as well as the exchange terms. Numerical calculations are conducted by minimizing the total magnetic energy from the determination of equilibrium static configurations. We consider experimental parameters found in the literature to illustrate our results for Fe/Cr/Fe trilayer systems. In particular, a total of six different magnetic scenarios are analyzed for three regimens of exchange fields and the [211] and [321] asymmetric growth directions. After numerically minimize the total energy, we use the equilibrium configurations to calculate magnetization and magnetoresistance curves with the respective magnetic phases and corresponding critical fields. These results are also used to establish the boundary for occurrence of saturated states. Within the context of the spin waves, we solve the equation of motion for these systems in order to find the respective associated dispersion relations. The results show similar magnetization and magnetoresistance curves for both [211] and [321] growth scenarios, including an equivalent magnetic transition behavior. However, the combination of those peculiar symmetries and influence of the exchange energies results in attractive properties, including the generation of magnetic states as a function of the asymmetric degree imposed in the [hkl] growth orientations. There is also an increasing incompatibility between the values of saturation fields of magnetization and magnetoresistance for the cases in which a magnetic field acts along intermediate cubic anisotropic axes, particularly in the situations where the bilinear and biquadratic exchange fields are comparable. The dispersion relations and static results are consistent, the corresponding magnetic states are also present in both acoustic and optical modes. Furthermore, Goldstone excitations are also observed for that particular cases of a magnetic field acting in the intermediate axes, an effect related to transitions of second order and to the spontaneous symmetry breaking imposed by the combination of the biquadratic energy with the cubic and uniaxial anisotropies.

Numerical study of the enlarged O(5) symmetry of the 3D antiferromagnetic RP^(2) spin model

We investigate by means of Monte Carlo simulation and finite-size scaling analysis the critical properties of the three dimensional O (5) non-linear σ model and of the antiferromagnetic RP^(2) model, both of them regularized on a lattice. High accuracy estimates are obtained for the critical exponents, universal dimensionless quantities and critical couplings. It is concluded that both models belong to the same universality class, provided that rather non-standard identifications are made for the momentum-space propagator of the RP^(2) model. We have also investigated the phase diagram of the RP^(2) model extended by a second-neighbor interaction. A rich phase diagram is found, where most of the phase transitions are of the first order.

Off-equilibrium fluctuation-dissipation relations in the 3d Ising spin glass in a magnetic field

We study the fluctuation-dissipation relations for a three dimensional Ising spin glass in a magnetic field both in the high temperature phase as well as in the low temperature one. In the region of times simulated we have found that our results support a picture of the low temperature phase with broken replica symmetry, but a droplet behavior cannot be completely excluded.

Practical engineering of hard spin-glass instances

Recent technological developments in the field of experimental quantum annealing have made prototypical annealing optimizers with hundreds of qubits commercially available. The experimental demonstration of a quantum speedup for optimization problems has since then become a coveted, albeit elusive goal. Recent studies have shown that the so far inconclusive results, regarding a quantum enhancement, may have been partly due to the benchmark problems used being unsuitable. In particular, these problems had inherently too simple a structure, allowing for both traditional resources and quantum annealers to solve them with no special efforts. The need therefore has arisen for the generation of harder benchmarks which would hopefully possess the discriminative power to separate classical scaling of performance with size from quantum. We introduce here a practical technique for the engineering of extremely hard spin-glass Ising-type problem instances that does not require "cherry picking" from large ensembles of randomly generated instances. We accomplish this by treating the generation of hard optimization problems itself as an optimization problem, for which we offer a heuristic algorithm that solves it. We demonstrate the genuine thermal hardness of our generated instances by examining them thermodynamically and analyzing their energy landscapes, as well as by testing the performance of various state-of-the-art algorithms on them. We argue that a proper characterization of the generated instances offers a practical, efficient way to properly benchmark experimental quantum annealers, as well as any other optimization algorithm.

Universal critical behavior of the two-dimensional Ising spin glass

We use finite size scaling to study Ising spin glasses in two spatial dimensions. The issue of universality is addressed by comparing discrete and continuous probability distributions for the quenched random couplings. The sophisticated temperature dependency of the scaling fields is identified as the major obstacle that has impeded a complete analysis. Once temperature is relinquished in favor of the correlation length as the basic variable, we obtain a reliable estimation of the anomalous dimension and of the thermal critical exponent. Universality among binary and Gaussian couplings is confirmed to a high numerical accuracy.

Application of Inelastic Neutron Scattering to the Methanol-to-Gasoline Reaction Over a ZSM-5 Catalyst

Peer reviewed

A facile spin-cast route for cation exchange of multilayer perpendicularly-aligned nanorod assemblies

A facile spin cast route was developed to convert perpendicularly aligned nanorod assemblies of cadmium chalcogenides into their silver and copper analogues. The assemblies are rapidly cation exchanged without affecting either the individual rod dimensions or collective superlattice order extending over several multilayers.

Ground and Electronic Excited States from Pairing Matrix Fluctuation and Particle-Particle Random Phase Approximation

The accurate description of ground and electronic excited states is an important and challenging topic in quantum chemistry. The pairing matrix fluctuation, as a counterpart of the density fluctuation, is applied to this topic. From the pairing matrix fluctuation, the exact electron correlation energy as well as two electron addition/removal energies can be extracted. Therefore, both ground state and excited states energies can be obtained and they are in principle exact with a complete knowledge of the pairing matrix fluctuation. In practice, considering the exact pairing matrix fluctuation is unknown, we adopt its simple approximation --- the particle-particle random phase approximation (pp-RPA) --- for ground and excited states calculations. The algorithms for accelerating the pp-RPA calculation, including spin separation, spin adaptation, as well as an iterative Davidson method, are developed. For ground states correlation descriptions, the results obtained from pp-RPA are usually comparable to and can be more accurate than those from traditional particle-hole random phase approximation (ph-RPA). For excited states, the pp-RPA is able to describe double, Rydberg, and charge transfer excitations, which are challenging for conventional time-dependent density functional theory (TDDFT). Although the pp-RPA intrinsically cannot describe those excitations excited from the orbitals below the highest occupied molecular orbital (HOMO), its performances on those single excitations that can be captured are comparable to TDDFT. The pp-RPA for excitation calculation is further applied to challenging diradical problems and is used to unveil the nature of the ground and electronic excited states of higher acenes. The pp-RPA and the corresponding Tamm-Dancoff approximation (pp-TDA) are also applied to conical intersections, an important concept in nonadiabatic dynamics. Their good description of the double-cone feature of conical intersections is in sharp contrast to the failure of TDDFT. All in all, the pairing matrix fluctuation opens up new channel of thinking for quantum chemistry, and the pp-RPA is a promising method in describing ground and electronic excited states.

The VLT-FLAMES Tarantula Survey XXI. Stellar spin rates of O-type spectroscopic binaries

Context: The initial distribution of spin rates of massive stars is a fingerprint of their elusive formation process. It also sets a key initial condition for stellar evolution and is thus an important ingredient in stellar population synthesis. So far, most studies have focused on single stars. Most O stars are, however, found in multiple systems. 

Aims: By establishing the spin-rate distribution of a sizeable sample of O-type spectroscopic binaries and by comparing the distributions of binary subpopulations with one another and with that of presumed-single stars in the same region, we aim to constrain the initial spin distribution of O stars in binaries, and to identify signatures of the physical mechanisms that affect the evolution of the spin rates of massive stars. 

Methods: We use ground-based optical spectroscopy obtained in the framework of the VLT-FLAMES Tarantula Survey (VFTS) to establish the projected equatorial rotational velocities (ν_esini) for components of 114 spectroscopic binaries in 30 Doradus. The ν_esini values are derived from the full width at half maximum (FWHM) of a set of spectral lines, using a FWHM vs. ν_esini calibration that we derive based on previous line analysis methods applied to single O-type stars in the VFTS sample. 

Results: The overall ν_esini distribution of the primary stars resembles that of single O-type stars in the VFTS, featuring a low-velocity peak (at ν_esini<200 kms^-1) and a shoulder at intermediate velocities (200 <ν_esini<300 kms^-1). The distributions of binaries and single stars, however, differ in two ways. First, the main peak at ν_esini ~ 100kms^-1 is broader and slightly shifted towards higher spin rates in the binary distribution than that of the presumed-single stars. This shift is mostly due to short-period binaries (P_orb~<10 d). Second, the ν_esini distribution of primaries lacks a significant population of stars spinning faster than 300 kms^-1, while such a population is clearly present in the single-star sample. The ν_esini distribution of binaries with amplitudes of radial velocity variation in the range of 20 to 200 kms^-1 (mostly binaries with P_orb ~ 10-1000 d and/or with q<0.5) is similar to that of single O stars below ν_esini_~<170kms^-1. 

Conclusions: Our results are compatible with the assumption that binary components formed with the same spin distribution as single stars, and that this distribution contains few or no fast-spinning stars. The higher average spin rate of stars in short-period binaries may either be explained by spin-up through tides in such tight binary systems, or by spin-down of a fraction of the presumed-single stars and long-period binaries through magnetic braking (or by a combination of both mechanisms). Most primaries and secondaries of SB2 systems with P_orb~<10 d appear to have similar rotational velocities. This is in agreement with tidal locking in close binaries where the components have similar radii. The lack of very rapidly spinning stars among binary systems supports the idea that most stars with ν_esini_~> 300kms^-1 in the single-star sample are actually spun-up post-binary interaction products. Finally, the overall similarities (low-velocity peak and intermediate-velocity shoulder) of the spin distribution of binary and single stars argue for a massive star formation process in which the initial spin is set independently of whether stars are formed as single stars or as components of a binary system.

Spin and spatial dynamics in electron-impact scattering off S-wave He using R-matrix with Time-Dependence theory

R-matrix with time-dependence theory is applied to electron-impact ionisation processes for He in the S-wave model. Cross sections for electron-impact excitation, ionisation and ionisation with excitation for impact energies between 25 and 225 eV are in excellent agreement with benchmark cross sections. Ultra-fast dynamics induced by a scattering event is observed through time-dependent signatures associated with autoionisation from doubly excited states. Further insight into dynamics can be obtained through examination of the spin components of the time-dependent wavefunction.

Non-Gaussian distribution of collective operators in quantum spin chains

We numerically analyse the behavior of the full distribution of collective observables in quantum spin chains. While most of previous studies of quantum critical phenomena are limited to the first moments, here we demonstrate how quantum fluctuations at criticality lead to highly non-Gaussian distributions. Interestingly, we show that the distributions for different system sizes collapse on thesame curve after scaling for a wide range of transitions: first and second order quantum transitions and transitions of the Berezinskii–Kosterlitz–Thouless type. We propose and analyse the feasibility of an experimental reconstruction of the distribution using light–matter interfaces for atoms in optical lattices or in optical resonators.