45 research outputs found
Influence of electron correlations on ground-state properties of III-V semiconductors
Lattice constants and bulk moduli of eleven cubic III-V semiconductors are
calculated using an ab initio scheme. Correlation contributions of the valence
electrons, in particular, are determined using increments for localized bonds
and for pairs and triples of such bonds; individual increments, in turn, are
evaluated using the coupled cluster approach with single and double
excitations. Core-valence correlation is taken into account by means of a core
polarization potential. Combining the results at the correlated level with
corresponding Hartree-Fock data, we obtain lattice constants which agree with
experiment within an average error of -0.2%; bulk moduli are accurate to +4%.
We discuss in detail the influence of the various correlation contributions on
lattice constants and bulk moduli.Comment: 4 pages, Latex, no figures, Phys. Rev. B, accepte
Correlated ab-initio calculations for ground-state properties of II-VI semiconductors
Correlated ab-initio ground-state calculations, using relativistic
energy-consistent pseudopotentials, are performed for six II-VI semiconductors.
Valence () correlations are evaluated using the coupled cluster approach
with single and double excitations. An incremental scheme is applied based on
correlation contributions of localized bond orbitals and of pairs and triples
of such bonds. In view of the high polarity of the bonds in II-VI compounds, we
examine both, ionic and covalent embedding schemes for the calculation of
individual bond increments. Also, a partitioning of the correlation energy
according to local ionic increments is tested. Core-valence ()
correlation effects are taken into account via a core-polarization potential.
Combining the results at the correlated level with corresponding Hartree-Fock
data we recover about 94% of the experimental cohesive energies; lattice
constants are accurate to \sim 1%; bulk moduli are on average 10% too large
compared with experiment.Comment: 10 pages, twocolumn, RevTex, 3 figures, accepted Phys. Rev.
Pseudo electron-deficient organometallics: limited reactivity towards electron-donating ligands
YesHalf-sandwich metal complexes are of considerable interest in medicine, material, and nanomaterial chemistry. The design of libraries of such complexes with particular reactivity and properties is therefore a major quest. Here, we report the unique and peculiar reactivity of eight apparently 16-electron half-sandwich metal (ruthenium, osmium, rhodium, and iridium) complexes based on benzene-1,2-dithiolato and 3,6-dichlorobenzene-1,2-dithiolato chelating ligands. These electron-deficient complexes do not react with electron-donor pyridine derivatives, even with the strong σ-donor 4-dimethylaminopyridine (DMAP) ligand. The Ru, Rh, and Ir complexes accept electrons from the triphenylphosphine ligand (σ-donor, π-acceptor), whilst the Os complexes were found to be the first examples of non-electron-acceptor electron-deficient metal complexes. We rationalized these unique properties by a combination of experimental techniques and DFT/TDFT calculations. The synthetic versatility offered by this family of complexes, the low reactivity at the metal center, and the facile functionalization of the non-innocent benzene ligands is expected to allow the synthesis of libraries of pseudo electron-deficient half-sandwich complexes with unusual properties for a large range of applications
A comprehensive study of Interatomic Coulombic Decay in argon dimers: Extracting R-dependent absolute decay rates from the experiment
In this work we present a comprehensive and detailed study of Interatomic Coulombic Decay (ICD) occurring after irradiating argon dimers with XUV-synchrotron radiation. A manifold of different decay channels is observed and the corresponding initial and final states are assigned. Additionally, the effect of nuclear dynamics on the ICD electron spectrum is examined for one specific decay channel. The internuclear distance-dependent width Γ(R) of the decay is obtained from the measured kinetic energy release distribution of the ions employing a classical nuclear dynamics model