We study strong correlation effects in a series of fused benzene rings (acenes) of varying length and width using our recently developed projected Hartree-Fock (PHF) method. These molecules, commonly known as polycyclic aromatic hydrocarbons or nanographenes, are very challenging for electronic structure theory because of their strong multireference character. This challenge is here met by PHF at moderate computational cost optimizing a spin eigenfunction obtained by projection of an unrestricted Hartree-Fock (UHF) trial determinant. The resulting method, known as SUHF, predicts that polyradical behavior and orbital entanglement are enhanced with molecular size, especially in systems whose structural motifs are dominated by zigzag edges, like oligoacenes.

Black phosphorus is a monatomic semiconducting layered material that degrades exothermically in the presence of light and ambient contaminants. Its degradation dynamics remain largely unknown. Even before degradation, local-probe studies indicate non-negligible local curvature—through a nonconstant height distribution—due to the unavoidable presence of intrinsic defects. We establish that these intrinsic defects are photo-oxidation sites because they lower the chemisorption barrier of ideal black phosphorus (>10 eV and out of visible-range light excitations) right into the visible and ultraviolet range (1.6 to 6.8 eV), thus enabling photoinduced oxidation and dissociation of oxygen dimers. A full characterization of the material’s shape and of its electronic properties at the early stages of the oxidation process is presented as well. This study thus provides fundamental insights into the degradation dynamics of this novel layered material.

The performance of the Heyd-Scuseria-Ernzerhorf (HSE) and single parameter long-range corrected Perdew-Burke-Ernzerhorf (LC-omegaPBE) range-separated hybrids for predicting magnetic coupling constants has been investigated for a broad set of magnetic molecular systems for which accurate experimental data exist. The set includes the H-He-H model system, two organic diradicals with different magnetic behaviors, and a series of Cu dinuclear complexes with a broad range of magnetic coupling values. Both HSE and LC-omegaPBE provide a significant improvement to standard hybrids such as the well-known hybrid Becke-3-parameters exchange with Lee-Yang-Parr correlation (B3LYP) functional. Nevertheless, the performance of these two range-separated hybrid functionals is different: HSE overestimates antiferromagnetic and ferromagnetic interactions in Cu dinuclear complexes (although significantly less than B3LYP), whereas LC-omegaPBE treats ferro- and antiferromagnetic couplings on a much more balanced way. The increased accuracy of LC-omegaPBE suggests that the inclusion of 100% Hartree-Fock exchange considered in the definition of this long-range corrected hybrid functional has important consequences for an accurate description of exchange and correlation effects on the electronic structure of open shell systems. On the other hand, HSE, which was developed with periodic systems in mind, also performs quite well (and better than B3LYP) thus opening the possibility of magnetic coupling studies in metal oxides and other challenging solids.

In realizing practical non-trivial topological electronic phases stable structures need to be determined first. Tin and lead do stabilize an optimal two-dimensional high-buckled phase --a hexagonal-close packed bilayer structure with nine-fold atomic coordination-- and they do not stabilize topological fullerenes, as demonstrated by energetics, phonon dispersion curves, and the structural optimization of finite-size samples. The high-buckled phases are metallic due to their high atomic coordination. The optimal structure of fluorinated tin lacks three-fold symmetry and it stabilizes small samples too. It develops two oblate conical valleys on the first Brillouin zone coupling valley, sublattice, and spin degrees of freedom with a novel $\tau_z\sigma_xs_x$ term, thus making it a new 2D platform for valleytronics.Comment: Submitted on 07/27/14. Accepted as a Rapid Communication on 11/20/1

We address the fundamental issue of growth of perovskite ultra-thin films under the condition of a strong polar mismatch at the heterointerface exemplified by the growth of a correlated metal LaNiO3 on the band insulator SrTiO3 along the pseudo cubic [111] direction. While in general the metallic LaNiO3 film can effectively screen this polarity mismatch, we establish that in the ultra-thin limit, films are insulating in nature and require additional chemical and structural reconstruction to compensate for such mismatch. A combination of in-situ reflection high-energy electron diffraction recorded during the growth, X-ray diffraction, and synchrotron based resonant X-ray spectroscopy reveal the formation of a chemical phase La2Ni2O5 (Ni2+) for a few unit-cell thick films. First-principles layer-resolved calculations of the potential energy across the nominal LaNiO3/SrTiO3 interface confirm that the oxygen vacancies can efficiently reduce the electric field at the interface.