Obtaining positions and widths of scattering resonances from a complex multiconfigurational self‐consistent field state using the M1 method

We present a complex multiconfigurational self‐consistent field (CMCSCF)‐based approach to investigate electron‐atom scattering resonances. It is made possible by the use of second quantization algebra adapted for biorthogonal spin orbitals, which has been applied to develop a quadratically convergent CMCSCF method. To control the convergence to the correct CMCSCF stationary point, a modified step‐length control algorithm is introduced. Convergence to a tolerance of 1.0 × 10^?10 a.u. for the energy gradient is found to be typically within 10 iterations or less. A method involving the first block of the M matrix defined in the multiconfigurational spin tensor electron propagator method (MCSTEP) based on the CMCSCF reference state has been implemented to investigate ²P Be^? shape resonances. The position and width of these resonances have been calculated for different complete active space choices. The wide distribution of the position and width of the resonance reported in the literature is explained by the existence of two distinct resonances which are close in energy. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Transient tertiary structure formation within the ribosome exit port

The exit tunnel of the ribosome is commonly considered to be sufficiently narrow that co-translational folding can begin only when specific segments of nascent chains are fully extruded from the tunnel. Here we show, on the basis of molecular simulations and comparison with experiment, that the long-range contacts essential for initiating protein folding can form within a nascent chain when it reaches the last 20 ? of the exit tunnel. We further show that, in this "exit port", a significant proportion of native and non-native tertiary structure can form without steric overlap with the ribosome itself, and provide a library of structural elements that our simulations predict can form in the exit tunnel and is amenable to experimental testing. Our results show that these elements of folded tertiary structure form only transiently and are at their midpoints of stability at the boundary region between the inside and the outside of the tunnel. These findings provide a framework for interpreting a range of recent experimental studies of ribosome nascent chain complexes and for understanding key aspects of the nature of co-translational folding.     

Isospin-violating dark matter in the Sun

We consider the prospects for studying spin-independent isospin-violating dark matter-nucleon interactions with neutrinos from dark matter annihilation in the Sun, with a focus on IceCube/DeepCore (IC/DC). If dark matter-nucleon interactions are isospin-violating, IC/DC?s reach in the spin-independent cross section may be competitive with current direct detection experiments for a wide range of dark matter masses. We also compare IC/DC?s sensitivity to that of next generation argon, germanium, neon and xenon based detectors.     

Interaction of the general volatile anesthetic Enflurane with bacteriorhodopsin-DPPC proteoliposomes

Thermal decomposition of dried crystalline powder obtained from titanium(IV) bis(acetylacetonate) diisopropoxide (75% solution in 2-propanol) (1) was monitored by simultaneous TG/DTA, EGA-FTIR and EGA-MS measurements and the results were compared with those of amorphous powder obtained by gelling of acetylacetonate-modified titanium(IV) tetra-isopropoxide at molar ratio of 1:2 in boiling 2-methoxyethanol (2). Thermal degradation of 1 in the temperature range of 25–700°C consists of 5 steps with a total mass loss of 62.5%. EGA by FTIR and MS revealed the release of H₂O below 120°C; followed by an intensive evolution of acetylacetone around 245°C. The release of acetone and acetic acid occurs up to 270°C and that of CO and CO₂ up to 530°C.     

Microstructure and Defect Characterization of Nanostructured Ni3Al

 Nanostructured Ni₃Al was produced by the inert gas condensation and in situ compaction technique and characterized by means of high-resolution transmission electron microscopy (HRTEM), X-ray diffraction, and density measurements. The defect structure was investigated using positron annihilation lifetime spectroscopy (PALS). It is shown that in some samples besides the cubic also the martensitic phase can be present. The defect structure can be divided into three major components: vacancy-like defects in the grain boundaries and nano-voids with a size of 1 nm as seen with PALS, and large pores with sizes up to 8 nm as seen with HRTEM. Furthermore, it is shown that an increasing compaction temperature leads to significantly smaller nano-voids.     

Hill‐climbing to Pasch valleys

Exhaustive enumeration of Steiner Triple Systems is not feasible, due to the combinatorial explosion of instances. The next‐best hope is to quickly find a sample that is representative of isomorphism classes. Stinson's Hill‐Climbing algorithm [ 20 ] is widely used to produce random Steiner Triple Systems, and certainly finds a sample of systems quickly, but the sample is not uniformly distributed with respect to the isomorphism classes of STS with ν ≤ 19, and, in particular, we find that isomorphism classes with a large number of Pasch configurations are under‐represented. No analysis of the non‐uniformity of the distribution with respect to isomorphism classes or the intractability of obtaining a representative sample for ν > 19 is known. We also exhibit a modification to hill‐climbing that makes the sample if finds closer to the uniform distribution over isomorphism classes in return for a modest increase in running time. © 2007 Wiley Periodicals, Inc. J Combin Designs 15: 405–419, 2007     

Slow flow of a non-Newtonian fluid past a micro-capsule

The streaming motion past a spherical microcapsule is studied. The particle consists of a thin elastic membrane enclosing an incompressible fluid. Since the problem is highly nonlinear, a perturbation solution is sought in the limiting case where the deviation from sphericity is small. Obviously, the capsule remains nearly spherical when λ, the ratio of viscous forces to elastic (shape-restoring) membrane forces is small. In this limit, the rheology of the inside fluid is immaterial and the problem is essentially characterized by three parameters: λ, the Reynolds number Re (interia effect), and the Weissenberg number We (non-newtonian effect). The deformation is obtained explicitly under the restriction We<1, Re<1. It is shown that to leading order, the capsule deforms exactly into a spheroid which can be either oblate or prolate, depending mainly upon the elasticity number We/Re: for We/Re<0.57 the spheroid is oblate, while for We/Re>0.81 a prolate spheroid results. For 0.57<We/Re<0.81 additional details of the rheology of the membrane and of the suspending fluid are needed. The degree of the deformation is governed by the parameters λ Re. All parameters of the problem enter into the expression of the drag force. On a qualitative basis, these results are similar to those for droplets although major differences exist quantitatively.     

A Flexible Photoactive Titanium Metal–Organic Framework Based on a [TiIV3(μ3‐O)(O)2(COO)6] Cluster

The synthesis of titanium–carboxylate metal–organic frameworks (MOFs) is hampered by the high reactivity of the commonly employed alkoxide precursors. Herein, we present an innovative approach to titanium‐based MOFs by the use of titanocene dichloride to synthesize COK‐69, the first breathing Ti MOF, which is built up from trans‐1,4‐cyclohexanedicarboxylate linkers and an unprecedented [Ti^IV₃(μ₃‐O)(O)₂(COO)₆] cluster. The photoactive properties of COK‐69 were investigated in depth by proton‐coupled electron‐transfer experiments, which revealed that up to one Ti^IV center per cluster can be photoreduced to Ti^III while preserving the structural integrity of the framework. The electronic structure of COK‐69 was determined by molecular modeling, and a band gap of 3.77 eV was found.     

Influence of Solution Volume on the Dissolution Rate of Silicon Dioxide in Hydrofluoric Acid

Experimental data and modeling of the dissolution of various Si/SiO₂ thermal coatings in different volumes of hydrofluoric acid (HF) are reported. The rates of SiO₂‐film dissolution, measured by means of various electrochemical techniques, and alteration in HF activity depend on the thickness of the film coating. Despite the small volumes (0.6–1.2 mL) of the HF solution, an effect of SiO₂‐coating thickness on the dissolution rate was detected. To explain alterations detected in HF activity after SiO₂ dissolution, spectroscopic analyses (NMR and FTIR) of the chemical composition of the solutions were conducted. This is associated with a modification in the chemical composition of the HF solution, which results in either the formation of an oxidized species in solution or the precipitation of dissolution products. HF₂^? accumulation in the HF solution, owing to SiO₂ dissolution was identified as the source of the chemical alteration.