Stoichiometric and catalytic oxygen activation by trimesityliridium(III)

Trimesityliridium(III) (mesityl = 2,4,6-trimethylphenyl) reacts with O(2) to form oxotrimesityliridium(V), (mes)(3)Ir=O, in a reaction that is cleanly second order in iridium. In contrast to initial reports by Wilkinson, there is no evidence for substantial accumulation of an intermediate in this reaction. The oxo complex (mes)(3)Ir=O oxidizes triphenylphosphine to triphenylphosphine oxide in a second-order reaction with DeltaH++ = 10.04 +/- 0.16 kcal/mol and DeltaS++ = -21.6 +/- 0.5 cal/(mol.K) in 1,2-dichloroethane. Triphenylarsine is also oxidized, though over an order of magnitude more slowly. Ir(mes)(3) binds PPh(3) reversibly (K(assoc) = 84 +/- 3 M(-1) in toluene at 20 degrees C) to form an unsymmetrical, sawhorse-shaped four-coordinate complex, whose temperature-dependent NMR spectra reveal a variety of dynamic processes. Oxygen atom transfer from (mes)(3)Ir=O and dioxygen activation by (mes)(3)Ir can be combined to allow catalytic aerobic oxidations of triphenylphosphine at room temperature and atmospheric pressure with overall activity (approximately 60 turnovers/h) comparable to the fastest reported catalysts. A kinetic model that uses the rates measured for dioxygen activation, atom transfer, and phosphine binding describes the observed catalytic behavior well. Oxotrimesityliridium does not react with sulfides, sulfoxides, alcohols, or alkenes, apparently for kinetic reasons.     

Sum-rules and Goldstone modes from extended random phase approximation theories in Fermi systems with spontaneously broken symmetries

The Self-Consistent RPA (SCRPA) approach is elaborated for cases with a continuouslybroken symmetry, this being the main focus of the present article. Correlations beyondstandard RPA are summed up correcting for the quasi-boson approximation in standard RPA.Desirable properties of standard RPA such as fulfillment of energy weighted sum rule andappearance of Goldstone (zero) modes are kept. We show theoretically and, for a modelcase, numerically that, indeed, SCRPA maintains all properties of standard RPA forpractically all situations of spontaneously broken symmetries. A simpler approximate formof SCRPA, the so-called renormalised RPA, also has these properties. The SCRPA equationsare first outlined as an eigenvalue problem, but it is also shown how an equivalent manybody Green’s function approach can be formulated.     

The optical potential of the deuteron (H3, He3) and the two (three) nucleon vibration coupling

We present a closed expression for the exact deuteron (H³, He³) optical potential in terms of higher point Green functions. This form is well suited to study its energy dependence. Intermediate resonances due to two (three) particle phonon coupling are suggested and the coupling constants are identified with the Migdal parameters.     

The imaginary part of the nucleon-nucleus optical potential in semiclassical approximation

We calculate in a novel Thomas-Fermi theory for multiparticle-multihole states the contributions of the correlation and polarization graphs to the imaginary part of the nucleon-nucleus optical potential $\text{W(ω,}\text{R}\text{,}\text{P}\text{)}$ depending on energy, radius and momentum. The present theory generalizes the older Fermi-gas and local-density approximations to this problem in the sense that we can assess precisely the validity of our approach. We show that it yields results which coincide with the average part of a corresponding quantal calculation. We use a gaussian finite-range effective interaction derived from the Gogny force and phenomenological mean-field potentials of the Woods-Saxon or harmonic-oscillator type. With these ingredients and no further adjustable parameters our results for the depth and volume integrals are in good agreement with the average trend of the elastic scattering data. Further, the resulting momentum dependence of W is strong, especially for small P. The influence of the Pauli principle is studied in detail.     

Light clusters in nuclear matter of finite temperature

We investigate properties and the distribution of light nuclei ( ) in symmetric nuclear matter of finite temperature within a microscopic framework. For this purpose we have solved few-body Alt-Grassberger-Sandhas-type equations for quasi-nucleons that include self-energy corrections and Pauli blocking in a systematic way. In a statistical model we find a significant influence in the composition of nuclear matter if medium effects are included in the microscopic calculation of nuclei. If multiplicities are frozen out at a certain time (or volume), we expect significant consequences for the formation of light fragments in a heavy ion collision. As a consequence of the systematic inclusion of medium effects, the ordering of multiplicities becomes opposite to the law-of-mass action of ideal components. This is necessary to explain the large abundance of -particles in a heavy ion collision that are otherwise largely suppressed in an ideal equilibrium scenario.PACS: 25.70.-z Low and intermediate energy heavy-ion reactions - 25.70.Pq Multifragment emission and correlations - 21.65. + f Nuclear matter - 21.45. + v Few-body systems     

Spin degrees of freedom and flattening of the spectra of single-particle excitations in strongly correlated Fermi systems

The impact of long-range spin-spin correlations on the structure of a flat portion in single-particle spectra ξ(p), which emerges beyond the point where the Landau state loses its stability, is studied. We supplement the well-known Nozieres model of a Fermi system with limited scalar long-range forces by a similar long-range spin-dependent term and calculate the spectra versus its strength g. It is found that Nozieres' results hold as long as g>0. However, with g changing its sign, the spontaneous magnetization is shown to arise at any nonzero g. The increase in the strength |g| is demonstrated to result in shrinkage of the domain in momentum space, occupied by the flat portion of ξ(p), and, eventually, in its vanishing.     

Self-consistent RPA based on a many-body vacuum

Self-Consistent RPA is extended in a way so that it is compatible with a variational ansatz for the ground-state wave function as a fermionic many-body vacuum. Employing the usual equation-of-motion technique, we arrive at extended RPA equations of the Self-Consistent RPA structure. In principle the Pauli principle is, therefore, fully respected. However, the correlation functions entering the RPA matrix can only be obtained from a systematic expansion in powers of some combinations of RPA amplitudes. We demonstrate for a model case that this expansion may converge rapidly.