Room temperature dynamic correlation between methylammonium molecules in lead-iodine based perovskites: An ab-initio molecular dynamics perspective

The high efficiency of lead organo-metal-halide perovskite solar cells has raised many questions about the role of the methylammonium (MA) molecules in the Pb-I framework. Experiments indicate that the MA molecules are able to 'freely' spin around at room temperature even though they carry an intrinsic dipole moment. We have performed large supercell (2592 atoms) finite temperature ab-initio molecular dynamics calculations to study the correlation between the molecules in the framework. An underlying long range anti-ferroelectric ordering of the molecular dipoles is observed. The dynamical correlation between neighboring molecules shows a maximum around room temperature in the mid-temperature phase. In this phase, the rotations are slow enough to (partially) couple to neighbors via the Pb-I cage. This results in a collective motion of neighboring molecules in which the cage acts as the mediator. At lower and higher temperatures the motions are less correlated

The random phase approximation applied to ice

Standard density functionals without van der Waals interactions yield an unsatisfactory description of ice phases, specifically, high density phases occurring under pressure are too unstable compared to the common low density phase I$_h$ observed at ambient conditions. Although the description is improved by using functionals that include van der Waals interactions, the errors in relative volumes remain sizable. Here we assess the random phase approximation (RPA) for the correlation energy and compare our results to experimental data as well as diffusion Monte Carlo data for ice. The RPA yields a very balanced description for all considered phases, approaching the accuracy of diffusion Monte Carlo in relative energies and volumes. This opens a route towards a concise description of molecular water phases on surfaces and in cavities

Anisotropic Magnetic Couplings and Structure-Driven Canted to Collinear Transitions in Spin-orbit Coupled Sr2IrO4

We put forward a scheme to study the anisotropic magnetic couplings in Sr2IrO4 by mapping fully relativistic constrained noncollinear density functional theory including an on-site Hubbard U correction onto a general spin model Hamiltonian. This procedure allows for the simultaneous account and direct control of the lattice, spin and orbital interactions within a fully ab initio scheme. We compute the isotropic, single site anisotropy and Dzyaloshinskii-Moriya (DM) coupling parameters, and clarify that the origin of the canted magnetic state in Sr2IrO4 arises from the interplay between structural distortions and the competition between isotropic exchange and DM interactions. A complete magnetic phase diagram with respect to the tetragonal distortion and the rotation of IrO6 octahedra is constructed, revealing the presence of two types of canted to collinear magnetic transitions: a spin-flop transition with increasing tetragonal distortion and a complete quenching of the basal weak ferromagnetic moment below a critical octahedral rotation

Relativistic GWGW+BSE study of the optical properties of Ruddlesden-Popper iridates

We study the optical properties of the Ruddlesden-Popper series of iridates Sr$_{n+1}$Ir$_n$O$_{3n+1}$ ($n$=1, 2 and $\infty$) by solving the Bethe-Salpeter equation (BSE), where the quasiparticle (QP) energies and screened interactions $W$ are obtained by the $GW$ approximation including spin-orbit coupling. The computed optical conductivity spectra show strong excitonic effects and reproduce very well the experimentally observed double-peak structure, in particular for the spin-orbital Mott insulators Sr$_2$IrO$_4$ and Sr$_3$Ir$_2$O$_7$. However, $GW$ does not account well for the correlated metallic state of SrIrO$_3$ owing to a much too small band renormalization, and this affects the overall quality of the optical conductivity. Our analysis describes well the progressive redshift of the main optical peaks as a function of dimensionality ($n$), which is correlated with the gradual decrease of the electronic correlation (quantified by the constrained random phase approximation) towards the metallic $n=\infty$ limit. We have also assessed the quality of a computationally cheaper BSE approach that is based on a model dielectric function and conducted on top of DFT+$U$ one-electron energies. Unfortunately, this model BSE approach does not accurately reproduce the outcome of the full $GW$+BSE method and leads to larger deviations to the measured spectra.Comment: 13 pages, 8 figure

Relação entre poda verde e o uso de material refletivo com a qualidade de pêssegos ´Eldorado´.

bitstream/item/33532/1/documento-134.pd

Exchange interactions and magnetic phases of transition metal oxides: benchmarking advanced ab initio methods

The magnetic properties of the transition metal monoxides MnO and NiO are investigated at equilibrium and under pressure via several advanced first-principles methods coupled with Heisenberg Hamiltonian MonteCarlo. The comparative first-principles analysis involves two promising beyond-local density functionals approaches, namely the hybrid density functional theory and the recently developed variational pseudo-self-interaction correction method, implemented with both plane-wave and atomic-orbital basis sets. The advanced functionals deliver a very satisfying rendition, curing the main drawbacks of the local functionals and improving over many other previous theoretical predictions. Furthermore, and most importantly, they convincingly demonstrate a degree of internal consistency, despite differences emerging due to methodological details (e.g. plane waves vs. atomic orbitals

Renyi Entropy of the XY Spin Chain

We consider the one-dimensional XY quantum spin chain in a transverse magnetic field. We are interested in the Renyi entropy of a block of L neighboring spins at zero temperature on an infinite lattice. The Renyi entropy is essentially the trace of some power $\alpha$ of the density matrix of the block. We calculate the asymptotic for $L \to \infty$ analytically in terms of Klein's elliptic $\lambda$ - function. We study the limiting entropy as a function of its parameter $\alpha$. We show that up to the trivial addition terms and multiplicative factors, and after a proper re-scaling, the Renyi entropy is an automorphic function with respect to a certain subgroup of the modular group; moreover, the subgroup depends on whether the magnetic field is above or below its critical value. Using this fact, we derive the transformation properties of the Renyi entropy under the map $\alpha \to \alpha^{-1}$ and show that the entropy becomes an elementary function of the magnetic field and the anisotropy when $\alpha$ is a integer power of 2, this includes the purity $tr \rho^2$. We also analyze the behavior of the entropy as $\alpha \to 0$ and $\infty$ and at the critical magnetic field and in the isotropic limit [XX model].Comment: 28 Pages, 1 Figur