Theoretical predictions of the electronic and optical properties of single and coupled (In,Ga)As/GaAs quantum dots

We show how an atomistic pseudopotential plus many-body configuration interaction theory can address the main spectroscopic features of self-assembled dots including, excitons, trions, biexcitons, fine-structure, charging spectra as well as electric-field dependence of entanglement in dot molecules.     

Long-range repulsive interaction between molecules on a metal surface induced by charge transfer

The adsorption of a molecular electron donor on Au(111) is characterized by the spontaneous formation of a superlattice of monomers spaced several nanometers apart. The coverage-dependent molecular pair distributions obtained from scanning tunneling microscopy data reveal an intermolecular long-range repulsive potential, which decreases as the inverse of the molecular separation. Density functional theory calculations show a charge accumulation in the molecules due to electron donation into the metal. Our results suggest that electrostatic repulsion between molecules persists on the surface of a metal.     

Quantitative Derivation of the Gross‐Pitaevskii Equation

Starting from first‐principle many‐body quantum dynamics, we show that the dynamics of Bose‐Einstein condensates can be approximated by the time‐dependent nonlinear Gross‐Pitaevskii equation, giving a bound on the rate of the convergence. Initial data are constructed on the bosonic Fock space applying an appropriate Bogoliubov transformation on a coherent state with expected number of particles N. The Bogoliubov transformation plays a crucial role; it produces the correct microscopic correlations among the particles. Our analysis shows that, on the level of the one‐particle reduced density, the form of the initial data is preserved by the many‐body evolution, up to a small error that vanishes as N^?1/2 in the limit of large N.© 2015 Wiley Periodicals, Inc.     

Iboga Inspired N-Indolylethyl-Substituted Isoquinuclidines as a Bioactive Scaffold: Chemoenzymatic Synthesis and Characterization as GDNF Releasers and Antitrypanosoma Agents

The first stage of the drug discovery process involves the identification of small compounds with biological activity. Iboga alkaloids are monoterpene indole alkaloids (MIAs) containing a fused isoquinuclidine-tetrahydroazepine ring. Both the natural products and the iboga-inspired synthetic analogs have shown a wide variety of biological activities. Herein, we describe the chemoenzymatic preparation of a small library of novel N-indolylethyl-substituted isoquinuclidines as iboga-inspired compounds, using toluene as a starting material and an imine Diels–Alder reaction as the key step in the synthesis. The new iboga series was investigated for its potential to promote the release of glial cell line-derived neurotrophic factor (GDNF) by C6 glioma cells, and to inhibit the growth of infective trypanosomes. GDNF is a neurotrophic factor widely recognized by its crucial role in development, survival, maintenance, and protection of dopaminergic neuronal circuitries affected in several neurological and psychiatric pathologies. Four compounds of the series showed promising activity as GDNF releasers, and a leading structure (compound 11) was identified for further studies. The same four compounds impaired the growth of bloodstream Trypanosoma brucei brucei (EC₅₀ 1–8 μM) and two of them (compounds 6 and 14) showed a good selectivity index.     

Self-assembling and phase coexistence of SW trimers as complex amphiphile analogues. I. Simulations

We analyse by discrete molecular dynamics the self-assembly of SW trimer particles that contain a different number of attractive and repulsive spheres. They also have different geometries: linear, obtuse, rectangular and equilateral. We identify that some of these molecules exhibit liquid–vapour equilibria while others do not. For all of them, we show the morphological phase diagram built up from the different supra-molecular structures formed by each type of trimer. We simulated 14 different systems with a total of 321 states. The main features of the supra-molecular structures depend only on the composition and geometry of the trimer: triple SW trimers do not form supra-structures, double SW trimers and single SW trimers form monolayers, bilayers and worm-like micelles. The liquid–vapour coexistence properties are also exhibited. These trimers can be used to model complex amphiphiles beyond the standard ones, such as the Gemini and the Bola surfactants as well as colloidal particles.     

Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols

The oxidation of alcohols with N₂O as the hydrogen acceptor was achieved with low catalyst loadings of a rhodium complex that features a cooperative bis(olefin)amido ligand under mild conditions. Two different methods enable the formation of either the corresponding carboxylic acid or the ester. N₂ and water are the only by‐products. Mechanistic studies supported by DFT calculations suggest that the oxygen atom of N₂O is transferred to the metal center by insertion into the Rh?H bond of a rhodium amino hydride species, generating a rhodium hydroxy complex as a key intermediate.     

Adiabatic corrections to density functional theory energies and wave functions

The adiabatic finite-nuclear-mass-correction (FNMC) to the electronic energies and wave functions of atoms and molecules is formulated for density-functional theory and implemented in the deMon code. The approach is tested for a series of local and gradient corrected density functionals, using MP2 results and diagonal-Born-Oppenheimer corrections from the literature for comparison. In the evaluation of absolute energy corrections of nonorganic molecules the LDA PZ81 functional works surprisingly better than the others. For organic molecules the GGA BLYP functional has the best performance. FNMC with GGA functionals, mainly BLYP, show a good performance in the evaluation of relative corrections, except for nonorganic molecules containing H atoms. The PW86 functional stands out with the best evaluation of the barrier of linearity of H2O and the isotopic dipole moment of HDO. In general, DFT functionals display an accuracy superior than the common belief and because the corrections are based on a change of the electronic kinetic energy they are here ranked in a new appropriate way. The approach is applied to obtain the adiabatic correction for full atomization of alcanes C(n)H(2n+2), n = 4-10. The barrier of 1 mHartree is approached for adiabatic corrections, justifying its insertion into DFT.     

Reduced Hamiltonians. II: The size-consistency of reduced Hamiltonians defined in model spaces

The link between the Absar-Coleman and the Valdemoro reduced Hamiltonian has been established. Further, a study of the size-consistency of approximations based on these Hamiltonians has been carried out. It is found that the energies obtained with reduced Hamiltonians that are defined in the full configuration interaction model spaces are not size consistent.     

Theoretical study of CeO2 and Ce2O3 using a screened hybrid density functional

The predicted structures and electronic properties of CeO(2) and Ce(2)O(3) have been studied using conventional and hybrid density functional theory. The lattice constant and bulk modulus for CeO(2) from local (LSDA) functionals are in good agreement with experiment, while the lattice parameter from a generalized gradient approximation (GGA) is too long. This situation is reversed for Ce(2)O(3), where the LSDA lattice constant is much too short, while the GGA result is in reasonable agreement with experiment. Significantly, the screened hybrid HSE functional gives excellent agreement with experimental lattice constants for both CeO(2) and Ce(2)O(3). All methods give insulating ground states for CeO(2) with gaps for the 4f band lying between 1.7 eV (LSDA) and 3.3 eV (HSE) and 6-8 eV for the conduction band. For Ce(2)O(3) the local and GGA functionals predict a semimetallic ground state with small (0-0.3 eV) band gap but weak ferromagnetic coupling between the Ce(+3) centers. By contrast, the HSE functional gives an insulating ground state with a band gap of 3.2 eV and antiferromagnetic coupling. Overall, the hybrid HSE functional gives a consistent picture of both the structural and electronic properties of CeO(2) and Ce(2)O(3) while treating the 4f band consistently in both oxides.