Advanced density functional theory methods for materials science

In this work we chiefly deal with two broad classes of problems in computational materials science, determining the doping mechanism in a semiconductor and developing an extreme condition equation of state. While solving certain aspects of these questions is well-trodden ground, both require extending the reach of existing methods to fully answer them. Here we choose to build upon the framework of density functional theory (DFT) which provides an efficient means to investigate a system from a quantum mechanics description.

Zinc Phosphide (Zn₃P₂) could be the basis for cheap and highly efficient solar cells. Its use in this regard is limited by the difficulty in n-type doping the material. In an effort to understand the mechanism behind this, the energetics and electronic structure of intrinsic point defects in zinc phosphide are studied using generalized Kohn-Sham theory and utilizing the Heyd, Scuseria, and Ernzerhof (HSE) hybrid functional for exchange and correlation. Novel 'perturbation extrapolation' is utilized to extend the use of the computationally expensive HSE functional to this large-scale defect system. According to calculations, the formation energy of charged phosphorus interstitial defects are very low in n-type Zn₃P₂ and act as 'electron sinks', nullifying the desired doping and lowering the fermi-level back towards the p-type regime. Going forward, this insight provides clues to fabricating useful zinc phosphide based devices. In addition, the methodology developed for this work can be applied to further doping studies in other systems.

Accurate determination of high pressure and temperature equations of state is fundamental in a variety of fields. However, it is often very difficult to cover a wide range of temperatures and pressures in an laboratory setting. Here we develop methods to determine a multi-phase equation of state for Ta through computation. The typical means of investigating thermodynamic properties is via ’classical’ molecular dynamics where the atomic motion is calculated from Newtonian mechanics with the electronic effects abstracted away into an interatomic potential function. For our purposes, a ’first principles’ approach such as DFT is useful as a classical potential is typically valid for only a portion of the phase diagram (i.e. whatever part it has been fit to). Furthermore, for extremes of temperature and pressure quantum effects become critical to accurately capture an equation of state and are very hard to capture in even complex model potentials. This requires extending the inherently zero temperature DFT to predict the finite temperature response of the system. Statistical modelling and thermodynamic integration is used to extend our results over all phases, as well as phase-coexistence regions which are at the limits of typical DFT validity. We deliver the most comprehensive and accurate equation of state that has been done for Ta. This work also lends insights that can be applied to further equation of state work in many other materials.

Relative energetics and structural properties of zirconia using a self-consistent tight-binding model

We describe an empirical, self-consistent, orthogonal tight-binding model for zirconia, which allows for the polarizability of the anions at dipole and quadrupole levels and for crystal field splitting of the cation d orbitals, This is achieved by mixing the orbitals of different symmetry on a site with coupling coefficients driven by the Coulomb potentials up to octapole level. The additional forces on atoms due to the self-consistency and polarizabilities are exactly obtained by straightforward electrostatics, by analogy with the Hellmann-Feynman theorem as applied in first-principles calculations. The model correctly orders the zero temperature energies of all zirconia polymorphs. The Zr-O matrix elements of the Hamiltonian, which measure covalency, make a greater contribution than the polarizability to the energy differences between phases. Results for elastic constants of the cubic and tetragonal phases and phonon frequencies of the cubic phase are also presented and compared with some experimental data and first-principles calculations. We suggest that the model will be useful for studying finite temperature effects by means of molecular dynamics.

Collapse versus growth for a Bose-Einstein condensate with attractive interactions

Using a model potential approach, we study the time-dependent behavior of a Bose-Einstein condensate with negative scattering length during its collapse in the zero-temperature limit. The condensate is modeled through an effective potential, which linearizes the Schrodinger equation, in order to obtain an intuitive visualization of the dynamics of the condensate. We find that a substantial fraction of the condensate survives the collapse. The origin for this survival is the reappearance of a barrier in the effective potential during the collapse. In contrast to previous calculations, the present calculations indicate that the size of the residual condensate strongly depends on the growth rate of the condensate. The present results are compared to other theoretical calculations and to experimental work.

Local temperature in quantum thermal states

We consider blocks of quantum spins in a chain at thermal equilibrium, focusing on their properties from a thermodynamical perspective. In a classical system the temperature behaves as an intensive magnitude, above a certain block size, regardless of the actual value of the temperature itself. However, a deviation from this behavior is expected in quantum systems. In particular, we see that under some conditions the description of the blocks as thermal states with the same global temperature as the whole chain fails. We analyze this issue by employing the quantum fidelity as a figure of merit, singling out in detail the departure from the classical behavior. As it may be expected, we see that quantum features are more prominent at low temperatures and are affected by the presence of zero-temperature quantum phase transitions. Interestingly, we show that the blocks can be considered indeed as thermal states with a high fidelity, provided an effective local temperature is properly identified. Such a result may originate from typical properties of reduced subsystems of energy-constrained Hilbert spaces. Finally, the relation between local and global temperatures is analyzed as a function of the size of the blocks and the system parameters.

Closure of the Monte Carlo dynamical equation in the spherical Sherrington-Kirkpatrick model

We study the analytical solution of the Monte Carlo dynamics in the spherical Sherrington-Kirkpatrick model using the technique of the generating function. Explicit solutions for one-time observables (like the energy) and two-time observables (like the correlation and response function) are obtained. We show that the crucial quantity which governs the dynamics is the acceptance rate. At zero temperature, an adiabatic approximation reveals that the relaxational behavior of the model corresponds to that of a single harmonic oscillator with an effective renormalized mass.

Large deviations of Rouse polymer chain: first passage problem

The purpose of this paper is to investigate several analytical methods of solving first passage (FP) problem for the Rouse model, a simplest model of a polymer chain. We show that this problem has to be treated as a multi-dimensional Kramers' problem, which presents rich and unexpected behavior. We first perform direct and forward-flux sampling (FFS) simulations, and measure the mean first-passage time $\tau(z)$ for the free end to reach a certain distance $z$ away from the origin. The results show that the mean FP time is getting faster if the Rouse chain is represented by more beads. Two scaling regimes of $\tau(z)$ are observed, with transition between them varying as a function of chain length. We use these simulations results to test two theoretical approaches. One is a well known asymptotic theory valid in the limit of zero temperature. We show that this limit corresponds to fully extended chain when each chain segment is stretched, which is not particularly realistic. A new theory based on the well known Freidlin-Wentzell theory is proposed, where dynamics is projected onto the minimal action path. The new theory predicts both scaling regimes correctly, but fails to get the correct numerical prefactor in the first regime. Combining our theory with the FFS simulations lead us to a simple analytical expression valid for all extensions and chain lengths. One of the applications of polymer FP problem occurs in the context of branched polymer rheology. In this paper, we consider the arm-retraction mechanism in the tube model, which maps exactly on the model we have solved. The results are compared to the Milner-McLeish theory without constraint release, which is found to overestimate FP time by a factor of 10 or more.

Universality of sudden death of entanglement

We present a constructive argument to demonstrate the universality of the sudden death of entanglement in the case of two non-interacting qubits, each of which generically coupled to independent Markovian environments at zero temperature. Conditions for the occurrence of the abrupt disappearance of entanglement are determined and, most importantly, rigourously shown to be almost always satisfied: Dynamical models for which the sudden death of entanglement does not occur are seen to form a highly idealized zero-measure subset within the set of all possible quantum dynamics.

Mean-field description of a dynamical collapse of a fermionic condensate in a trapped boson-fermion mixture

We suggest a time-dependent dynamical mean-field-hydrodynamic model for the collapse of a trapped boson-fermion condensate and perform numerical simulation based on it to understand some aspects of the experiment by Modugno et al. [Science 297, 2240 (2002)] on the collapse of the fermionic condensate in the K-40-Rb-87 mixture. We show that the mean-field model explains the formation of a stationary boson-fermion condensate at zero temperature with relative sizes compatible with experiment. This model is also found to yield a faithful representation of the collapse dynamics in qualitative agreement with experiment. In particular we consider the collapse of the fermionic condensate associated with (a) an increase of the number of bosonic atoms as in the experiment and (b) an increase of the attractive boson-fermion interaction using a Feshbach resonance. Suggestion for experiments of fermionic collapse using a Feshbach resonance is made.

Quark condensates and high density quark matter

We consider a Coulomb gauge quark model which includes an explicit construct for a nontrivial vacuum structure in QCD. The dynamics is described by a Hamiltonain that contains a linearly rising confining potential and longitudinal and transverse Coulomb-type interactions. The Coulomb potential gives rise to ultraviolate divergences which are non-perturbatively renormalized by adding appropriate counter terms to the Hamiltonian. The equation of state for u and d quark matter at zero temperature is derived in the Hartree-Fock approximation.

Superfluid Bose-Fermi mixture from weak coupling to unitarity

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nonlinear Schrodinger equation for a superfluid Fermi gas in the BCS-BEC crossover

We introduce a quasianalytic nonlinear Schrodinger equation with beyond mean-field corrections to describe the dynamics of a zero-temperature dilute superfluid Fermi gas in the crossover from the weak-coupling Bardeen-Cooper-Schrieffer (BCS) regime, where k(F)parallel to a parallel to << 1 with a the s-wave scattering length and k(F) the Fermi momentum, through the unitarity limit k(F)a ->+/-infinity to the Bose-Einstein condensation (BEC) regime where k(F)a > 0. The energy of our model is parametrized using the known asymptotic behavior in the BCS, BEC, and the unitarity limits and is in excellent agreement with accurate Green's-function Monte Carlo calculations. The model generates good results for frequencies of collective breathing oscillations of a trapped Fermi superfluid.

Nonlinear Schrodinger equation for a superfluid Bose gas from weak coupling to unitarity: Study of vortices

We introduce a nonlinear Schrodinger equation to describe the dynamics of a superfluid Bose gas in the crossover from the weak-coupling regime, where an(1/3)<<1 with a the interatomic s-wave scattering length and n the bosonic density, to the unitarity limit, where a ->+infinity. We call this equation the unitarity Schrodinger equation (USE). The zero-temperature bulk equation of state of this USE is parametrized by the Lee-Yang-Huang low-density expansion and Jastrow calculations at unitarity. With the help of the USE we study the profiles of quantized vortices and vortex-core radius in a uniform Bose gas. We also consider quantized vortices in a Bose gas under cylindrically symmetric harmonic confinement and study their profile and chemical potential using the USE and compare the results with those obtained from the Gross-Pitaevskii-type equations valid in the weak-coupling limit. Finally, the USE is applied to calculate the breathing modes of the confined Bose gas as a function of the scattering length.

HEAT-KERNEL EXPANSION AT FINITE TEMPERATURE

We show how the zero-temperature result for the heat-kernel asymptotic expansion can be generalized to the finite-temperature one. We observe that this general result depends on the interesting ratio square-root tau/beta, where tau is the regularization parameter and beta = 1/T, so that the zero-temperature limit beta --> infinity corresponds to the cutoff limit tau --> 0. As an example, we discuss some aspects of the axial model at finite temperature.

CHIRAL SCHWINGER MODEL WITH A PODOLSKY TERM AT FINITE-TEMPERATURE

We study an exactly solvable two-dimensional model which mimics the basic features of the standard model. This model combines chiral coupling with an infrared behavior which resembles low energy QCD. This is done by adding a Podolsky higher-order derivative term in the gauge field to the Lagrangian of the usual chiral Schwinger model. We adopt a finite temperature regularization procedure in order to calculate the non-trivial fermionic Jacobian and obtain the photon and fermion propagators, first at zero temperature and then at finite temperature in the imaginary and real time formalisms. Both singular and non-singular cases, corresponding to the choice of the regularization parameter, are treated. In the nonsingular case there is a tachyonic mode as usual in a higher order derivative theory, however in the singular case there is no tachyonic excitation in the spectrum.

Anisotropy in the transport properties of type II superconducting films with periodic pinning

Using numerical simulations, we analyze the anisotropy effects in the critical currents and dynamical properties of vortices in a thin superconducting film submitted to hexagonal and Kagomé periodical pinning arrays. The calculations are performed at zero temperature, for transport currents parallel and perpendicular to the main axis of the lattice, and parallel to the diagonal axis of the rhombic unit cell. We show that the critical currents and dynamic properties are anisotropic for both pinning arrays and all directions of the transport current. The anisotropic effects are more significant just above the critical current and disappear with higher values of current and both pinning arrays. The dynamical phases for each case and a wide range of transport forces are analyzed. © 2012 Springer Science+Business Media, LLC.