46 research outputs found
The Nature of the Interlayer Interaction in Bulk and Few-Layer Phosphorus
An outstanding challenge of theoretical electronic structure is the
description of van der Waals (vdW) interactions in molecules and solids.
Renewed interest in resolving this is in part motivated by the technological
promise of layered systems including graphite, transition metal
dichalcogenides, and more recently, black phosphorus, in which the interlayer
interaction is widely believed to be dominated by these types of forces. We
report a series of quantum Monte Carlo (QMC) calculations for bulk black
phosphorus and related few-layer phosphorene, which elucidate the nature of the
forces that bind these systems and provide benchmark data for the energetics of
these systems. We find a significant charge redistribution due to the
interaction between electrons on adjacent layers. Comparison to density
functional theory (DFT) calculations indicate not only wide variability even
among different vdW corrected functionals, but the failure of these functionals
to capture the trend of reorganization predicted by QMC. The delicate interplay
of steric and dispersive forces between layers indicate that few-layer
phosphorene presents an unexpected challenge for the development of vdW
corrected DFT.Comment: 8 pages, 6 figure
Relative importance of crystal field versus bandwidth to the high pressure spin transition in transition metal monoxides
The crystal field splitting and d bandwidth of the 3d transition metal
monoxides MnO, FeO, CoO and NiO are analyzed as a function of pressure within
density functional theory. In all four cases the 3d bandwidth is significantly
larger than the crystal field splitting over a wide range of compressions. The
bandwidth actually increases more as pressure is increased than the crystal
field splitting. Therefore the role of increasing bandwidth must be considered
in any explanation of a possible spin collapse that these materials may exhibit
under pressure.Comment: 7 pages, 4 figure