We have analyzed the structure and bonding of gas-phase Cl-X and [HCl-X](+) complexes for X(+)= H(+), CH3 (+), Li(+), and Na(+), using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl(-) and HCl for the various cations. The Cl-X bond becomes longer and weaker along X(+) = H(+), CH3 (+), Li(+), and Na(...

The electronic structure, Non-Linear Optical (NLO) properties and Natural Bonding Orbital (NBO) analysis of 1,4-dioxane were investigated using the theoretical study of Density Functional Theory (DFT) calculations at the B3LYP/6-311G (d,p) level of theory. The optimized structure is nonlinear as indicated from the dihedral angles.  Natural bonding orbital analysis has been analyzed in terms...

Through a basis-set-independent web of localizing orbital-transformations, the electronic wave function of a molecule is expressed in terms of a set of orbitals that reveal the atomic structure and the bonding pattern of a molecule. The analysis is based on resolving the valence orbital space in terms of an internal space, which has minimal basis set dimensions, and an external space. In the in...

The electronic structure of metal-organic interfaces is of paramount importance for the properties of organic electronic and single-molecule devices. Here, we use so-called orbital overlap populations derived from slab-type band-structure calculations to analyze the covalent contribution to the bonding between an adsorbate layer and a metal. Using two prototypical molecules, the strong acceptor...

We report the study of small lithium clusters Lin(0/+1/)(-)(1) (n = 5-7), performed via the novel Gradient Embedded Genetic Algorithm (GEGA) technique and molecular orbital analysis. GEGA was developed for searching of the lowest-energy structures of clusters. Results of our search, obtained using this program, have been compared with the previous ab initio calculations, and the efficiency of t...

Density Functional Theory (DFT) calculations have been carried out using a Polarizable Continuum Model (PCM) in an attempt to investigate the electro-molecular properties of branched-chain glucoside (C14C10-D-glucoside) isomers. The results showed that αconfiguration of pyranoside form is thermodynamically the most stable, while the solution should contain much more β...

The importance of relativity and dispersion in metallophilicity has been discussed in numerous studies. The existence of hybridization in the bonding between closed shell d10-d10 metal atoms has also been speculated, but the presence of attractive MO interaction in the metal-metal bond is still a matter of an ongoing debate. In this comparative study, a quantitative molecular orbital analysis a...

During the last twenty years the Polyhedral Skeletal Electron Pair Theory and the isolobal analogy have provided a theoretical basis for the rapid experimental developments, which have occurred in metal cluster chemistry. These theoretical principles have been underpinned by m.o. calculations on specific molecules and more generally by the Tensor Surface Harmonic Theory. This paper will review ...

The striking differences observed in the electron-induced (EI) mass fragmentation pathways of two isomeric benzodipyrans are attributable to hydrogen bonding in these molecules. In the "angular" isomer, 6-butyryl-5-hydroxy-2,2,8,8-tetramethyl-3,4,9,10-tetra-hydro-2H,8H-benzo[1,2-b:3,4-b(1)]dipyran (2), H-bonding occurs between the aromatic OH group and the alpha carbonyl moiety contained in the...