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

Evidence for the weakly coupled electron mechanism in an Anderson-Blount polar metal

Over 50 years ago, Anderson and Blount proposed that ferroelectric-like structural phase transitions may occur in metals, despite the expected screening of the Coulomb interactions that often drive polar transitions. Recently, theoretical treatments have suggested that such transitions require the itinerant electrons be decoupled from the soft transverse optical phonons responsible for polar order. However, this decoupled electron mechanism (DEM) has yet to be experimentally observed. Here we utilize ultrafast spectroscopy to uncover evidence of the DEM in LiOsO_3, the first known band metal to undergo a thermally driven polar phase transition (T_c ≈ 140 K). We demonstrate that intra-band photo-carriers relax by selectively coupling to only a subset of the phonon spectrum, leaving as much as 60% of the lattice heat capacity decoupled. This decoupled heat capacity is shown to be consistent with a previously undetected and partially displacive TO polar mode, indicating the DEM in LiOsO_3

Fermi-surface pockets in magnetic underdoped cuprates from first principles

Using an innovative first-principles band theory enabling the exploration of Mott-insulating magnetic cuprates, we study the Fermi surface of underdoped Y$_{1-x}$Ca$_x$Ba$_2$Cu$_3$O$_6$ in a selection of magnetically ordered and polaronic states. All phases exhibit qualitatively similar, hole-like nodal-point small pockets. Their properties (area, masses, mass sign) only partially match those extracted from recent quantum-oscillation experiments. Ab initio calculations, therefore, do not straightforwardly support a magnetic origin of quantum oscillations.Comment: 4 pages, 4 figure

Diazotroph Activity in Surface Narragansett Bay Sediments in Summer is Stimulated by Hypoxia and Organic Matter Delivery

Bacteria that carry out many processes of the nitrogen cycle inhabit estuarine sediments. Denitrification is known to be a dominant process causing estuarine sediments to behave as net nitrogen sinks. However, measurements of nitrogen fluxes in the sediments of Narragansett Bay, Rhode Island, USA, have at times revealed high rates of net nitrogen (N2) fixation. Whereas changes in primary production, in magnitude and phenology, within Narragansett Bay have been identified as possible causes for these changes in nitrogen cycling within the benthos, a factor that has not been examined thus far is seasonal hypoxia. Since anaerobic diazotrophs figure so prominently within the sediments of Narragansett Bay, we hypothesized that dissolved oxygen concentrations in the bottom waters affect their activity. In order to explore this relationship, we measured the activity of diazotrophs in the surface sediments of 3 study areas during the summers of 2013 and 2014 using the acetylene reduction assay. We explored the effects of several water quality parameters on nitrogenase activity including, among others, dissolved oxygen and chlorophyll concentrations. Our measurements of nitrogenase activity were generally low, ranging between 2 and 5 nmol ethylene g-1 d-1 but spiked to 16 nmol ethylene g-1 d-1 at an area experiencing severe hypoxia in July 2013. Our data suggest that diazotrophy in estuarine sediments is enhanced when the benthos experiences very low dissolved oxygen in conjunction with recent influxes of autochthonous organic matter. Experiments with sediment core incubations conducted in the laboratory support our hypothesis that low dissolved oxygen and organic matter additions promote N2 fixation

A variational pseudo-self-interaction correction approach: ab-initio description of correlated oxides and molecules

We present a fully variational generalization of the pseudo self-interaction correction (VPSIC) approach previously presented in two implementations based on plane-waves and atomic orbital basis set, known as PSIC and ASIC, respectively. The new method is essentially equivalent to the previous version for what concern the electronic properties, but it can be exploited to calculate total-energy derived properties as well, such as forces and structural optimization. We apply the method to a variety of test cases including both non-magnetic and magnetic correlated oxides and molecules, showing a generally good accuracy in the description of both structural and electronic properties.Comment: 23 pages, 9 tables, 16 figure