A journey inside the U28 nanocapsule.

Anionic uranyl-peroxide U(28) nanocapsules trap cations and other anions inside, whose structures cannot be resolved by X-ray diffraction, owing to crystallographic disorder. DFT calculations enabled the complete characterization of the geometry of these complex systems and also explained the origin of the disorder. The stability of the capsules was strongly influenced by the entrapped cations.

A density-functional study of the adsorption of methane-thiol on the (111) surfaces of the Ni-group metals: II. Vibrational spectroscopy.

The vibrational eigenstates of methane-thiol (CH(3)SH) and methane-thiolate (CH(3)S) in the gas phase and in dense monolayers adsorbed on the (111) surfaces of the Ni-group metals have been investigated within the framework of density-functional theory using generalized response and force-constant techniques. For isolated CH(3)SH good agreement of eigenfrequencies and intensities with the measured infrared spectra is achieved. For the CH(3)S radical, experimental information from laser-induced fluorescence spectroscopy is available only for selected eigenmodes.

A density functional study of the adsorption of methane-thiol on the (111) surfaces of the Ni-group metals: I. Molecular and dissociative adsorption.

The molecular and dissociative adsorption of methane-thiol (CH(3)SH) in the high-coverage limit on the (111) surfaces of the Ni-group metals has been investigated using ab initio density functional techniques. In molecular form, methane-thiol is bound to the surface only by weak polarization-induced forces in a slightly asymmetric configuration with the C-S axis tilted by 35-60° relative to the surface normal. On Ni and Pd surfaces the S atom occupies a position close to a bridge site; on Pt it is located close to an on-top position.

The platinum-olefin binding energy in series of (PH3)2Pt(olefin) complexes--a theoretical study.

Theoretical investigation of Pt(0)-olefin organometallic complexes containing tertiary phosphine ligands was focused on the strength of platinum-olefin electronic interaction. DFT theoretical study of electronic effects in a substantial number of ethylene derivatives was evaluated in terms of the Pt-olefin binding energy using MP2 correlation theory. Organometallics bearing coordinated olefins with general formula (R1R2C = CR3R4)Pt(PH3)2 [R = various substituents] had been selected, including olefins containing both electron-donor substituents as well as electron-withdrawing groups.