Molybdenite (MoS2) undergoes a transition from an indirect to direct gap semiconductor exhibiting strong photoluminescence when confined in a 2D monolayer. We investigate the effect of interlayer interactions on the band structure and density of states using the screened hybrid functional of Heyd, Scuseria, and Ernzerhof. We show that for the bulk and monolayer systems, our short-range screened hybrid functional produces band gaps in good agreement with experiment. Our functional includes only interlayer interactions of non-van der Waals origin, predicts properties consistent with recent experiments, and provides predictions for few-layered systems.

We explore the concept of seniority number (defined as the number of unpaired electrons in a determinant) when applied to the problem of electron correlation in atomic and molecular systems. Although seniority is a good quantum number only for certain model Hamiltonians (such as the pairing Hamiltonian), we show that it provides a useful partitioning of the electronic full configuration interaction (FCI) wave function into rapidly convergent Hilbert subspaces whose weight diminishes as its seniority number increases. The primary focus of this study is the adequate description of static correlation effects. The examples considered are the ground states of the helium, beryllium, and neon atoms, the symmetric dissociation of the N(2) and CO(2) molecules, as well as the symmetric dissociation of an H(8) hydrogen chain. It is found that the symmetry constraints that are normally placed on the spatial orbitals greatly affect the convergence rate of the FCI expansion. The energy relevance of the seniority zero sector (determinants with all paired electrons) increases dramatically if orbitals of broken spatial symmetry (as those commonly used for Hubbard Hamiltonian studies) are allowed in the wave function construction.

We derive and implement symmetry-projected Hartree-Fock-Bogoliubov (HFB) equations and apply them to the molecular electronic structure problem. All symmetries (particle number, spin, spatial, and complex conjugation) are deliberately broken and restored in a self-consistent variation-after-projection approach. We show that the resulting method yields a comprehensive black-box treatment of static correlations with effective one-electron (mean-field) computational cost. The ensuing wave function is of multireference character and permeates the entire Hilbert space of the problem. The energy expression is different from regular HFB theory but remains a functional of an independent quasiparticle density matrix. All reduced density matrices are expressible as an integration of transition density matrices over a gauge grid. We present several proof-of-principle examples demonstrating the compelling power of projected quasiparticle theory for quantum chemistry.

Chemical signatures correlated with uranium oxide processing are of interest to forensic science for inferring sample provenance. Identification of temporal changes in chemical structures of process uranium materials as a function of controlled temperatures and relative humidities may provide additional information regarding sample history. In this study, a high-purity α-U3O8 sample and three other uranium oxide samples synthesized from reaction routes used in nuclear conversion processes were stored under controlled conditions over 2-3.5 years, and powder X-ray diffraction analysis and X-ray absorption spectroscopy were employed to characterize chemical speciation. Signatures measured from the α-U3O8 sample indicated that the material oxidized and hydrated after storage under high humidity conditions over time. Impurities, such as uranyl fluoride or schoepites, were initially detectable in the other uranium oxide samples. After storage under controlled conditions, the analyses of the samples revealed oxidation over time, although the signature of the uranyl fluoride impurity diminished. The presence of schoepite phases in older uranium oxide material is likely indicative of storage under high humidity and should be taken into account for assessing sample history. The absence of a signature from a chemical impurity, such as uranyl fluoride hydrate, in an older material may not preclude its presence at the initial time of production. LA-UR-15-21495.

The UHF wave function may be written as a spin-contaminated pair wave function of the APSG form, and the overlap of the α and β corresponding orbitals of the UHF solution can be taken as a proxy for the strength of the correlation captured by breaking symmetry. We demonstrate this with calculations on one- and two-dimensional hydrogen clusters and make contact with the well studied Hubbard model. The UHF corresponding orbitals pair in a manner that allows a smooth evolution from doubly occupied orbitals at small distance to one in which wave function breaks symmetry, segregating the α and β electrons onto distinct sublattices at large distances. By performing spin projection on these UHF solutions, we address strong correlations that are difficult to capture at intermediate distances using a single determinant.