A GGA plus U approach to effective electronic correlations in thiolate-ligated iron-oxo (IV) porphyrin

High-valent oxo-metal complexes exhibit correlated electronic behavior on dense, low-lying electronic state manifolds, presenting challenging systems for electronic structure methods. Among these species, the iron-oxo (IV) porphyrin denoted Compound I occupies a privileged position, serving a broad spectrum of catalytic roles. The most reactive members of this family bear a thiolate axial ligand, exhibiting high activity toward molecular oxygen activation and substrate oxidation. The default approach to such systems has entailed the use of hybrid density functionals or multi-configurational/multireference methods to treat electronic correlation. An alternative approach is presented based on the GGA+U approximation to density functional theory, in which a generalized gradient approximation (GGA) functional is supplemented with a localization correction to treat on-site correlation as inspired by the Hubbard model. The electronic structure of thiolate-ligated iron-oxo (IV) porphyrin and corresponding Coulomb repulsion U are determined both empirically and self-consistently, yielding spin-distributions, state level splittings, and electronic densities of states consistent with prior hybrid functional calculations. Comparison of this detailed electronic structure with model Hamiltonian calculations suggests that the localized 3d iron moments induce correlation in the surrounding electron gas, strengthening local moment formation. This behavior is analogous to strongly correlated electronic systems such as Mott insulators, in which the GGA+U scheme serves as an effective single-particle representation for the full, correlated many-body problem

Crystal structure, Hirshfeld surface analysis and computational studies of (E)-2,2-dimethyl-4-styryl-2,3-dihydro-1H-benzo[b][1,4]diazepine

The crystal structure, Hirshfeld surface analysis, and computational studies of (E)-2,2-dimethyl-4-styryl-2,3-dihydro-1H-benzo[b][1,4]diazepine have been presented. The compound crystallized in the monoclinic space group P21/c with 8 molecules in it unit cell. A comparison of the experimental and computed bond lengths and bond angles showed good agreement among the results with varying deviations from each other. A discussion of the Hirshfeld surface analysis of the compound have been carried out to provide insight into the structural properties of the compound

Synthesis, characterization and crystal structures of two new phenolic mannich bases

Two new Mannich bases, 5-methyl-2-((4-(pyridin-2-yl)piperazin-1-yl)methyl)phenol (1) and 5-methyl-2-((4-(4-nitrophenyl)piperazin-1-yl)methyl)phenol (2), were prepared and characterized structurally with elemental analysis, IR, UV and NMR spectroscopic techniques as well as single crystal X-ray diffraction. Compound I crystallizes in the monoclinic space group P21/c with unit cell dimensions a = 6.6726(2) Å, b =   17.0542(6)   Å, c = 13.3222(4) Å, β = 100.832(1)°, V = 1489.00 (8) Å3, Z = 4, R1 = 0.0408, wR2 = 0.1143. Compound II crystallizes in the monoclinic space P21 with unit cell dimensions a = 5.9519(2) Å, b = 17.3315(8) Å, c = 15.7237(7) Å, β = 90.348(2)°, V = 1621.95(12) Å3, Z = 4, R1 = 0.0353, wR2 = 0.0965. Both compounds have their structures stabilized by hydrogen bonding and π∙∙∙π interactions.               KEY WORDS: Mannich base, Piperazine, X-ray diffraction, Hydrogen bonds Bull. Chem. Soc. Ethiop. 2019, 33(2), 341-348.DOI: https://dx.doi.org/10.4314/bcse.v33i2.1

Synthesis, characterization and DPPH scavenging activity of some benzimidazole derivatives

A base-catalyzed conversion of aldehydes to benzimidazoles has been achieved. The compounds have been characterized by IR, NMR, micoranalysis, and GC-MS. The reaction for the formation of benzimidazoles has been monitored with 1H NMR and IR. The crystal structures of two derivatives, 2-(2-chlorophenyl)-1H-benzimidazole and 2-(1H-benzimidazol-2-yl)-4-nitrophenol, are presented. A study of the DPPH scavenging activity of these compounds showed that 2-(1H-benzimidazol-2-yl)phenol (2), 2-p-tolyl-1H-benzimidazole (3) and 2-(4-methoxyphenyl)-1H-benzimidazole (7) gave IC50 values 1974, 773 and 800 µM.               KEY WORDS: Benzimidazole, o-Phenylenediamine, Aldehydes, Base catalysis, DPPH scavenging activity Bull. Chem. Soc. Ethiop. 2018, 32(2), 271-284.DOI: https://dx.doi.org/10.4314/bcse.v32i2.

Vegetation Change from the Euro-American Settlement Era to the Present in Relation to Environment and Disturbance in Southwest Oregon

Faced with landscapes degraded by fire suppression, logging, and grazing, land managers in the interior western US are attempting to restore habitat structure and function. In southwest Oregon, landscape-scale fuels treatments are being implemented with goals including recreating historic vegetation structure, despite poor understanding of the nature of the landscape prior to widespread Euro-American influence, or the patterns and processes of vegetation change over time. We compared a General Land Office-based reconstruction of Euro-American settlement era (1850s) vegetation in southwest Oregon's interior valleys and foothills with modern vegetation interpreted from aerial orthoimages to determine patterns of vegetation distribution in both eras, trajectories of vegetation change, and environmental and disturbance factors related to these themes. We found that this landscape was primarily occupied by closed plant community types in both eras, with a comparatively minor proportion in open types; vegetation was distributed along a dominant environmental gradient that ran from prairies in xeric lowlands to conifer forests in steeper, cooler uplands. Temporal shifts from open to closed vegetation were consistent with expected effects of fire suppression in many cases, but in other cases, the long-term persistence of open vegetation in the absence of recorded fire indicated that other mechanisms were also in operation. Human encroachment into wildlands, particularly in valleys, has also been a major driver of landscape-level change in the past 150 yr. Our results suggest that conservation should focus on lowlands, particularly where uncommon vegetation types such as savanna, shrubland, and prairie still exist.Keywords: vegetation distribution, Klamath-Siskiyou region, General Land Office surveys, southwest Oregon, environmental gradient

Free expansion of two-dimensional condensates with a vortex

We study the free expansion of a pancake-shaped Bose-condensed gas, which is initially trapped under harmonic confinement and containing a vortex at its centre. In the case of a radial expansion holding fixed the axial confinement we consider various models for the interactions, depending on the thickness of the condensate relative to the value of the scattering length. We are thus able to evaluate different scattering regimes ranging from quasi-three-dimensional (Q3D) to strictly two-dimensional (2D). We find that as the system goes from Q3D to 2D the expansion rate of the condensate increases whereas that of the vortex core decreases. In the Q3D scattering regime we also examine a fully free expansion in 3D and find oscillatory behaviour for the vortex core radius: an initial fast expansion of the vortex core is followed by a slowing down. Such a nonuniform expansion rate of the vortex core may be taken into account in designing new experiments.Comment: 10 pages, 4 figure

(2E)-3-(6-Methoxynaphthalen-2-yl)-1-(pyridin-3-yl)prop-2-en-1-one and its cyclocondensation product with guanidine, (4RS)-2-amino-4-(6-methoxynaphthalen-2-yl)-6-(pyridin-3-yl)-3,4-dihydropyrimidine monohydrate: Two types of hydrogen-bonded sheet

The structures of a chalcone and of its cyclo­condensation product with guanidine are reported. In (2E)-3-(6-meth­oxy­naphthalen-2-yl)-1-(pyridin-3-yl)prop-2-en-1-one, C19H15NO2, (I), the planes of the pyridine and naphthalene units make dihedral angles with that of the central spacer unit of 23.61 (13) and 23.57 (15)°, respectively, and a dihedral angle of 47.24 (9)° with each other. The mol­ecules of (I) are linked into sheets by a combination of C-H...O and C-H...[pi](arene) hydrogen bonds. In the cyclo­condensation product (4RS)-2-amino-4-(6-meth­oxy­naphthalen-2-yl)-6-(pyri­din-3-yl)-3,4-dihydro­pyrimidine monohydrate, C20H18N4O·H2O, (II), the di­hydro­pyrimidine ring adopts a conformation best described as a shallow boat. The mol­ecular components are linked by two N-H...O hydrogen bonds, two O-H...N hydrogen bonds and one N-H...N hydrogen bond to form complex sheets, with the meth­oxy­naphthalene inter­digitated between inversion-related pairs of sheets

Demonstration of quantum Zeno effect in a superconducting phase qubit

Quantum Zeno effect is a significant tool in quantum manipulating and computing. We propose its observation in superconducting phase qubit with two experimentally feasible measurement schemes. The conventional measurement method is used to achieve the proposed pulse and continuous readout of the qubit state, which are analyzed by projection assumption and Monte Carlo wave-function simulation, respectively. Our scheme gives a direct implementation of quantum Zeno effect in a superconducting phase qubit.Comment: 5 pages, 4 figure

Quantum Optical Systems for the Implementation of Quantum Information Processing

We review the field of Quantum Optical Information from elementary considerations through to quantum computation schemes. We illustrate our discussion with descriptions of experimental demonstrations of key communication and processing tasks from the last decade and also look forward to the key results likely in the next decade. We examine both discrete (single photon) type processing as well as those which employ continuous variable manipulations. The mathematical formalism is kept to the minimum needed to understand the key theoretical and experimental results