Validating additive correction schemes against gradient-based extrapolations

The use of additive correction schemes to obtain structures and vibrational frequencies of increasingly larger molecules is becoming more common. Such approaches, based on the cubic extrapolation formula applied directly to the quantity of interest, have been successfully validated only at the highest levels of computational accuracy: for coupled cluster methods with comparably large basis sets. Here, a systematic validation of geometries and vibrational frequencies is carried out, including more affordable and relevant levels of theory, such as the Møller-Plesset perturbation theory applied with smaller basis sets. Comparisons of such additive schemes against the more rigorous gradient-based extrapolation are presented. The cbs () routine of the open-source quantum-chemistry package Psi4 has been extended for this purpose. The results confirm that geometries and frequencies of covalently bound species obtained with additive correction schemes are in an excellent agreement with the results of gradient-based extrapolations. However, when applied to systems involving noncovalent interactions, the errors due to such schemes are significantly larger. In general, we propose the application of gradient-based extrapolations, as they incur no extra cost compared to additive schemes.     

CPMD Simulation of a Bimolecular Chemical Reaction: Nucleophilic Attack of a Disulfide Bond under Mechanical Stress

Previous single‐molecule atomic force microscopy (AFM) experiments showed a change in the reactivity of a bimolecular substitution reaction with a definite force acting on a protein containing disulfide bonds. Using Car–Parrinello molecular dynamics (CPMD) simulations, we analyse the relevant reaction pathways for the breaking of a disulfide bond in the presence of nucleophiles.     

A two-sided short-recurrence extended Krylov subspace method for nonsymmetric matrices and its relation to rational moment matching

The Lagrange interpolation problem on spaces of symmetric bivariate polynomials is considered to reduce the interpolation problem to problems of approximately half dimension. The Berzolari-Radon construction is adapted to these kinds of problems by considering nodes placed on symmetric lines or symmetric pairs of lines. A Newton formula for the symmetric interpolant using the Berzolari-Radon construction is proposed.     

Donorstabilized Monometaphosphates and Phosphonates- Structure,Bonding, and Reactivity

Abstract

Previoudy we reported on the preparative use of donorstabilized monometaphosphates, Py.PO₂Cl and Py.PS₂Cl[¹]. ³P MAS investigations as well as X-ray single crystal analysis have been carried out. The isotropic chemical shift of the sulfur compound shows the typical downfield shift (106 ppm) with respect to the oxygen compound The chemical shift anisotropy gives additional information. The relative large spans ω (Py.PO₂Cl: 401 ppm, Py.PS₂Cl: 461 ppm) [²] reveal strong deviations from tetrahedral symmetry (ω = 0 ppm) in agreement with the structural data. The values of the skew parametem K (0.64 and 0.71 resp.) reflect the trend to axial symmetry (k = ± l). X-ray diffraction and NMR data suggest a structural model corresponding to a concentration of double bond character on the two P-X bonds. This model is consistent with the extremely short P-X bond length (1.449 Å and 1.921 Å rasp.) as well as the large P-X-P bond angles (126.4°and 123.7° resp.).     

Anomalous lattice response at the Mott transition in a quasi-2D organic conductor

Discontinuous changes of the lattice parameters at the Mott metal-insulator transition are detected by high-resolution dilatometry on deuterated crystals of the layered organic conductor kappa-(BEDT-TTF)(2)Cu[N(CN)(2)]Br. The uniaxial expansivities uncover a striking and unexpected anisotropy, notably a zero effect along the in-plane c axis along which the electronic interactions are relatively strong. A huge thermal expansion anomaly is observed near the end point of the first-order transition line enabling us to explore the critical behavior with very high sensitivity. The analysis yields critical fluctuations with an exponent alpha approximately 0.8+/-0.15 at odds with the novel criticality recently proposed for these materials [Kagawa et al., Nature (London) 436, 534 (2005)]. Our data suggest an intricate role of the lattice degrees of freedom in the Mott transition for the present materials.     

Acid‐Catalyzed Oxidative Radical Addition of Ketones to Olefins

Based on a mechanistic study, we have discovered a Brønsted acid catalyzed formation of ketone radicals. This is believed to proceed via thermally labile alkenyl peroxides formed in situ from ketones and hydroperoxides. The discovery could be utilized to develop a multicomponent radical addition of unactivated ketones and tert‐butyl hydroperoxide to olefins. The resulting γ‐peroxyketones are synthetically useful intermediates that can be further transformed into 1,4‐diketones, homoaldol products, and alkyl ketones. A one‐pot reaction yielding a pharmaceutically active pyrrole is also described.     

Review of the analytical techniques for sesquiterpenes and sesquiterpene lactones

In this paper the analytical techniques of about the last 2 decades for sesquiterpenes including their lactones are reviewed. For sesquiterpenes, methods like GC, GC-EI-MS, GC-CI-MS, GC-MS-MS, GC-FT-IR, GC-UV, GC-AES, 13C-NMR, PY-GC-MS, HPLC, HPLC-TSP, SFE, SFC, SFC-UV are available, GC combined with MS is the most widespread. Sesquiterpene lactones can be analysed by HPLC, HPLC-TSP, HPLC-APCI, HPLC-ESI, HPLC-PB, HPLC-NMR, SFC, MEKC, GC, GC-MS, TLC and OPLC. Here HPLC is the method of choice. The usefulness of the individual methods are briefly discussed.     

The conductivity of a two-dimensional electronic system of finite width in the presence of a strong perpendicular magnetic field and a random potential

Starting from the Kubo formula the conductivity tensor of a two-dimensional electronic system in a perpendicular magnetic field is evaluated. It is shown that at zero temperature only the states at the Fermi level contribute. The Hall conductivity of a purely periodic system of finite width is calculated and compared with earlier suggestions by Thouless et al. For a system described by a periodic and a random potential the Hall conductivity is calculated as a function of the electron density. The results emphasize the importance of disorder independent current carrying states for the Quantum Hall effect which extend along the boundaries of the system. The plateaux values of the Hall conductivity are related to the number of these states, and are independent of the existence of extended bulk states below the Fermi energy.