On the Donor Ability of the Phosphaneiminato Substituent and Cube Formation with Transition Metal Fragments

The particular role of the phosphaneiminato ligand as a donor is investigated for a) nitrenes (phosphinidenes) and carbenes and b) cubane formation with transition metals. Accordingly, and as shown for the case a) the ligand is a stronger π‐donor than an amino group and can be considered as a special case of imine‐type substituents. The latter are very effective in π‐donation. In the case b), i.e. the cubane formation with transition metals, one has to consider transition metals with a partially or completely filled d‐shell (with electrons). Hence depending on the transition metal, cubanes are build with weak ferromagnetic coupled or closed shell systems. For the cubanes with closed shell character the matter of insertion of halide anions is discussed. In the last chapter of the review the bond stretching in the dithionitrosyl complexes with rhenium is characterized.     

Kinetics and equilibrium of small metallic clusters: Ab initio confinement molecular dynamics study of 4

The ab initio molecular dynamics (AIMD) [1] is combined with the heuristic, successive confinement method of surveying a potential energy surface (PES) [2], thereby offering a framework for the simulation study of kinetics and equilibrium properties of metallic clusters. This approach is applied to the study of Au₄, a cluster possessing a simple but specific PES, which consists of very shallow and deep basins and due to this presents a challenge to the conventional AIMD methods. Among other things, the probabilities of the transitions between isomers have been found, and on this basis, both the time-dependent and equilibrium populations of the isomers have been calculated for the conditions typical of the NeNePo experiments [3] in the femtosecond pump-probe spectroscopy.     

Theoretical study of peptide model dimers. Homo versus heterochiral complexes

The study of possible chiral recognition of a series of peptide models (For-Gly-NH₂, For-Ala-NH₂ and four of their fluoro substituted derivatives) has been carried out by means of DFT calculations. Homo (L,L) and heterochiral (L,D) dimers formed by hydrogen bond (HB) complexation have been considered. Initially, the conformational preferences of the monomers have been calculated and used to generate all the possible homo and heterochiral dimers. The energetic results show that in most cases, the β monomers are the most stable while in the dimers, the γ–γ complexes show the strongest interaction energies. In three of the four chiral cases studied, a heterochiral dimer is the most stable one. In addition, the electron density and nuclear shielding of the complexes have been studied.     

Topological analysis of charge density in heptasulfur imide (S7NH) from isolated molecule to solid

Intra and intermolecular interactions of heptasulfur imide (S₇NH) are investigated in terms of topological properties analyses, such analyses are applied to both experimental (multipole model) and theoretically calculated (DFT and PDFT calculations) charge densities of the isolated molecule and of the crystal. The same analyses are also applied to a multipole model density obtained from theoretically (PDFT) derived structural amplitudes. The covalent bond character of S-N, N-H and S-S bonds are well described in terms of density, ρ_b, and total energy density, H_b, at the bond critical point r_c, though it is clear that the S-S bonds are weaker shared interactions than those of N-H and S-N bonds. Lone pair electron regions of sulfur and nitrogen atoms are revealed as the local charge concentration site from the Laplacian of charge density. The even weaker intermolecular interactions are well characterized; these include the N-H?S hydrogen bonding, N?S binding interactions and S?S binding interactions. All these intermolecular binding interactions are closed-shell interactions. The Laplacian of charge density demonstrates a directional intermolecular binding interaction. The corresponding intermolecular binding energies are derived by MP2/6-311+G(d,p) calculations. Atomic graph of each atom of the molecule is described in detail by the vertices, edges and faces of the polyhedron around the nucleus to illustrate such directional interactions.     

A first-principles study of surface and subsurface H on and in Ni(1 1 1): diffusional properties and coverage-dependent behavior

Periodic, self-consistent, density functional theory (GGA-PW91) calculations are performed for both surface and subsurface atomic hydrogen on and in Ni(1 1 1). At a low coverage (θ=0.25 ML), the binding energies (BEs) of a hydrogen atom in surface fcc, subsurface octahedral (first layer), and subsurface octahedral (second layer) sites are −2.89, −2.18, and −2.11 eV, respectively. The activation energy barriers for hydrogen diffusion from the surface to the first subsurface layer and from the first to the second subsurface layer are estimated to be 0.88 and 0.52 eV, respectively. In the entire coverage range studied, hydrogen occupies surface fcc and hcp sites and subsurface octahedral sites. In addition, the magnitude of the BE per hydrogen atom and the magnetization of the nickel slabs both decrease as hydrogen coverage increases. Vibrational frequencies of hydrogen at various surface and subsurface sites are calculated and are in reasonable agreement with experimental data. A phase stability calculation with a 2 × 2 surface unit cell shows that a p(2 × 2)-2H overlayer structure (θ=0.5 ML) and a p(1 × 1)-1H structure (θ=1.0 ML) are stable at low hydrogen pressures, in agreement with numerous experimental results. A very large increase in pressure is required to populate subsurface sites. After such an increase occurs, the first subsurface layer is filled completely.     

Quantum-Chemical Study of the Profiles of Reactions that Form Pyrrole Anion N-Adducts with CS<Subscript>2</Subscript> and CO<Subscript>2</Subscript>

The profiles of reactions leading to pyrrole anion N-adducts with CO₂ and CS₂ have been studied by the ab initio (RHF/6-31+G*, MP2/6-31+G*) and density functional (B3LYP/6-31+G*) methods. Addition of the pyrrole anion to the carbon disulfide molecule is accompanied by the appearance of a minimum corresponding to a pre-reaction complex. The transformation of the complex to the N-pyrrolyldithiocarboxylate anion occurs via a low activation barrier, which is due to repolarization of the C=S bonds. The profile of the reaction leading to the pyrrole anion N-adduct with CO₂ does not contain any intermediate stationary points throughout the whole route from reagents to products.Original Russian Text Copyright © 2004 by V. B. Kobychev, N. M. Vitkovskaya, I. L. Zaitseva, and B. A. Trofimov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 990–993, November–December, 2004.     

A density functional theory computational study of the role of ligand on the stability of CuI and CuII species associated with ATRP and SET‐LRP

Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with Cu^I and trigonal bipyramidal with axial halide complexes with [Cu^IIX]⁺ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [Cu^IIX]⁺ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [Cu^IIX]⁺ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007     

Particle multiplicities in the fission-like reactions of 340 MeV Si on Th

Pre-scission and post-scission multiplicities of neutrons and alpha particles have been simultaneously measured for the fission-like reactions of 340 MeV ²⁸Si on ²³²Th. Dynamical model calculations using HICOL code predict that about 90% of the observed events are of quasi-fission type while the remaining 10% are from compound nucleus fission decay. Moving source fits were carried out to the observed neutron and alpha particle spectra, measured at different angles with respect to the fragment directions. The pre-scission and post-scission neutron multiplicities are deduced to be 8.7±2.0 and 9.4±2.0, respectively. The corresponding multiplicity values for alpha particles are found to be 0.22±0.08 and 0.1±0.03. From the measured post-scission neutron multiplicity, it is inferred that about 65±20 MeV of the initial excitation energy remains at scission. This may be compared to the value of 85±30 MeV estimated from PACE2 statistical model calculations, adjusted to reproduce the measured pre-scission neutron multiplicity. From a comparison of the Statistical Model predictions with the measured pre-scission neutron multiplicity, the fission delay is estimated to be of 5⁺⁷₋₃×10⁻²⁰ s which overlaps with the average duration of fission-like process from the contact to the scission point (2×10⁻²⁰ s) as determined from HICOL-based dynamical calculations. For the delay time deduced as above, the pre-scission alpha particle multiplicity calculated by the PACE2 code is about a factor two larger than the experimental one, demonstrating the difficulties in modelling the alpha particle emission from highly elongated shapes that characterize the fissioning system from the contact point to scission.