We have carried out a theoretical investigation of the methylalkalimetal monomers CH3M and tetramers (CH3M)4 with M = Li, Na, K, and Rb and, for comparison, the methyl halides CH3X with X = F, Cl, Br, and I, using density functional theory (DFT) at BP86/TZ2P. Our purpose is to determine how the structure and thermochemistry (e.g., C-M bond lengths and strengths, oligomerization energies) of org...

The electron paramagnetic resonance of copper (II)-tetram m ine nitrate in solution of methanol and water has been investigated. The data obtained from the spectra at room tem perature and 97 °K together with the optical transition energies determined from single crystal polarized absorption spectra at 77 °K by other authors were used to calculate the LCAO-MO bonding parameters. The bonding orb...

Don't be square! A rare S(4) (2-) rectangle bridging two M(2)Cp(2)(mu(2)-CH(2))(2) (M=Rh, Ir) fragments is found to contain two "half-bonds" with S-S distances of 2.70 or 2.90 A. Computational studies explore the connection between these "half-bonds" and a Jahn-Teller distortion, as well as possible intermediates that form M(4)S(4) (2+) clusters having the S(4) (2-) rectangle rotated by 90 degr...

We have investigated the molecular geometries of a series of dicoordinated d(10)-transition-metal complexes ML2 (M=Co(-), Rh(-), Ir(-), Ni, Pd, Pt, Cu(+), Ag(+), Au(+); L=NH3, PH3, CO) using relativistic density functional theory (DFT) at ZORA-BLYP/TZ2P. Not all complexes have the expected linear ligand-metal-ligand (L-M-L) angle: this angle varies from 180° to 128.6° as a function of the metal...

The unreported brucinium benzilate (BBA) crystal and Hirshfeld surface analysis indicated the influence of intramolecular hydrogen bonding network on structure. Protonation occurs at tertiary nitrogen as it is most basic site. protonated N-H+ proton was observed 7.08 ppm carbon COO- 178.41 ppm. Molecular electrostatic potential (MEP) studies showed electron-rich electron-deficient sites in mole...

The imidoiron(IV) species are relatively less explored compared to the oxoiron(IV) intermediates. Recently, generation and characterization of a novel imido/oxoiron(iv) species ([(N(4)Py)Fe(IV)=X](2+) X = NTs; 1, O; 2) has been reported with an S = 1 ground state. Although the ground state for 1 and 2 are the same, they are reported to be distinctly different in other aspects. Unlike the oxoiro...

Aqueous chloride solutions are ubiquitous and diverse; systems include sea water, atmospheric droplets, geological processes and biological organisms. However, despite considerable effort, a complete microscopic model of the hydration shell, and local electronic structure of the aqueous chloride ion and its dynamics has not been established. In this work we employ ab initio molecular dynamics t...

COVER PICTURE Lando P. Wolters and F. Matthias Bickelhaupt* The cover picture illustrates the authors' quantum chemical finding that π electrons can significantly bend otherwise linear d(10)-ML2 complexes through backbonding. The foreground features a typical series of linear and nonlinear computed equilibrium geometries, while, in the background, one discerns quantitative numerical output of t...

the density functional theory (dft) and the natural bond orbital (nbo) calculations basedmethod b3lyp/6-31g* were carried out to study the interaction of carbon nanotube (8,0) withnitrobenzene in two situations perpendicular and parallel. formation energies of compounds,charges, the highest occupied molecular orbital (homo) and the lowest unoccupied molecular'orbital (lumo) and the homo-lumo ba...