LOBSTER: Local orbital projections,atomic charges,and chemical-bonding analysis from projector-augmented-wave-based density-functional theory

We present an update on recently developed methodology and functionality in the computer program Local Orbital Basis Suite Toward Electronic-Structure Reconstruction (LOBSTER) for chemical-bonding analysis in periodic systems. LOBSTER is based on an analytic projection from projector-augmented wave (PAW) density-functional theory (DFT) computations (Maintz et al., J. Comput. Chem. 2013 , 34, 2557), reconstructing chemical information in terms of local, auxiliary atomic orbitals and thereby opening the output of PAW-based DFT codes to chemical interpretation. We demonstrate how LOBSTER has been improved by taking into account time-reversal symmetry, thereby speeding up the DFT and LOBSTER calculations by a factor of 2. Over the recent years, the functionalities have also been continually expanded, including accurate projected densities of states (DOSs), crystal orbital Hamilton population (COHP) analysis, atomic and orbital charges, gross populations, and the recently introduced k -dependent COHP. The software is offered free-of-charge for non-commercial research.     

Preparation of a chiral azadiene for the synthesis of 5-aza analogues of angucyclinones

We have developed an efficient synthesis of both enantiomers of a key azadiene for the preparation of 5-aza analogues of angucyclinones through a hetero Diels-Alder reaction. These dienes were efficiently prepared via a 4-step procedure from known and readily available chiral diketoesters.     

Prompt γ-ray emission in the reactions of 120 MeV 20Ne with 27A1

The emission of prompt γ-radiation in the de-excitation of the products of the reactions of 120 MeV ²⁰Ne with ²⁷Al has been studied. Three NaI detectors placed at angles of 35°, 90° and 145° to the direction of the ²⁰Ne beam were used to detect γ-rays in coincidence with reaction products having 6 ≦ Z ≦ 20, detected in a counter telescope. Data were obtained with the counter telescope in the same plane, as well as in a plane perpendicular to the plane defined by the beam and the NaI detectors. The average multiplicities 〈M_γ〉, average energies 〈E_γ〉, primary γ-ray energy spectra and the variation of 〈M_γ〉 and 〈E_γ〉 with angle of observation and kinetic energy of the detected products are presented and discussed in terms of the dominant reaction mechanisms.     

Local convergence of some iterative methods for generalized equations

We study generalized equations of the following form:

(render)

0f(x)+g(x)+F(x),

where f is Fréchet differentiable in a neighborhood of a solution x^* of (*) and g is Fréchet differentiable at x^* and where F is a set-valued map acting in Banach spaces. We prove the existence of a sequence (x_k) satisfying

which is super-linearly convergent to a solution of (*). We also present other versions of this iterative procedure that have superlinear and quadratic convergence, respectively.     

Axiomatizing the Harsanyi solution,the symmetric egalitarian solution and the consistent solution for NTU-games

The validity of the axiomatization of the Harsanyi solution for NTU-games by Hart (1985) is shown to depend on the regularity conditions imposed on games. Following this observation, we propose two related axiomatic characterizations, one of the symmetric egalitarian solution (Kalai and Samet, 1985) and one of the consistent solution (Maschler and Owen, 1992). The three axiomatic results are studied, evaluated and compared in detail.Revised October 2004We thank an anonymous referee and an associate editor for their helpful comments. Geoffroy de Clippel also thanks Professors Sergiu Hart, Jean-François Mertens and Enrico Minelli. Horst Zank thanks the Dutch Science Foundation NWO and the British Council for support under the UK-Netherlands Partnership Programme in Science (PPS 706). The usual disclaimer applies.     

Asymmetric synthesis of the cyclopentanones related to NCS and N1999A2 antitumor antibiotics

Optically pure protected mono- or dihydroxylated cyclopentanones, precursors for the core of the antitumor antibiotics NCS and N1999A2, 1 and 2, were obtained in six to eight steps with excellent overall yields (up to 52%).     

Cover Picture

The cover picture shows the metalloporphyrin heterodimer [(tpp)Mo$\rm{\mathop{-}^{4}}$Re(oep)](+) with the novel [Mo$\rm{\mathop{-}^{4}}$Re](5+) core. The core represents the first example of a quadruple bond between elements of different triads, thus proving that heterometallic quadruple bonds are not limited to the Group 6 metals. From the space-filling model it is clear that there is no interaction between the stabilizing porphyrin ligands. The ORTEP plot in a projection along the Re-Mo axis emphasizes the perfectly eclipsed geometry of the porphyrins, which is unambiguous proof of the existence of the quadruple bond in the solid state. The diamagnetism and large magnetic anisotropy of the cation, as determined by (1)H NMR spectroscopy, indicate that the quadruple bond is retained in solution. A logical and well-defined synthetic route was used to synthesize the dimer, and can be extended to other metalloporphyrins to generate further novel quadruple bonds (the picture was generated by Marina Boulan, St. Petersburg, Russia), full details are reported by J. P. Collman et al. on p. 1271 ff.     

An axiomatization of the inner core

We axiomatize the inner core in a similar way as the one proposed by Aumann (1985) in order to characterize the NTU value. Received: March 2002/Revised: March 2003