Theoretical investigation of product channels in the CH3O2 + Br reaction

Several reaction pathways on the potential energy surface (PES) for the reaction of CH3O2 radicals with Br atoms are examined using both ab initio and density functional methods. Analysis of the PES suggests the presence of the stable intermediates CH3OOBr and CH3OBrO. CH3OOBr is calculated to be more stable than CH3OBrO by 9.7 kcal mol(-1) with a significant barrier preventing formation of CH3OBrO via isomerization of CH3OOBr. The relative importance of bi- and termolecular product channels resulting from the initially formed CH3OOBr adduct are assessed based on calculated barriers to the formation of CH2OO + HBr, CH3O + BrO, CH3Br + O2, and CH2O + HOBr.     

The Generalized Pairs Plot

This article develops a generalization of the scatterplot matrix based on the recognition that most datasets include both categorical and quantitative information. Traditional grids of scatterplots often obscure important features of the data when one or more variables are categorical but coded as numerical. The generalized pairs plot offers a range of displays of paired combinations of categorical and quantitative variables. A mosaic plot, fluctuation diagram, or faceted bar chart may be used to display two categorical variables. A side-by-side boxplot, stripplot, faceted histogram, or density plot helps visualize a categorical and a quantitative variable. A traditional scatterplot is suitable for displaying a pair of numerical variables, but options also support density contours or annotating summary statistics such as the correlation and number of missing values, for example. By combining these, the generalized pairs plot may help to reveal structure in multivariate data that otherwise might go unnoticed in the process of exploratory data analysis. Two different R packages provide implementations of the generalized pairs plot, gpairs and GGally. Supplementary materials for this article are available online on the journal web site.     

Recognition Properties and Self‐assembly of Planar [M(2‐pyridyl‐1,2,3‐triazole)2]2+ Metallo‐ligands

Molecular recognition continues to be an area of keen interest for supramolecular chemists. The investigated [M( L )₂]²⁺ metallo‐ligands (M=Pd^II, Pt^II, L =2‐(1‐(pyridine‐4‐methyl)‐1 H‐1,2,3‐triazol‐4‐yl)pyridine) form a planar cationic panel with vacant pyridyl binding sites. They interact with planar neutral aromatic guests through π–π and/or metallophilic interactions. In some cases, the metallo‐ligands also interacted in the solid state with Ag^I either through coordination to the pendant pyridyl arms, or through metal–metal interactions, forming coordination polymers. We have therefore developed a system that reliably recognises a planar electron‐rich guest in solution and in the solid state, and shows the potential to link the resultant host–guest adducts into extended solid‐state structures. The facile synthesis and ready functionalisation of 2‐pyridyl‐1,2,3‐triazole ligands through copper(I)‐catalyzed azide–alkyne cycloaddition (CuAAC) “click” chemistry should allow for ready tuning of the electronic properties of adducts formed from these systems.     

Dislocation-phonon interaction

The recent result that uniform screw dislocation motion can be sustained by an applied stress s < 10^?5 initiates a study of the influence of intrinsic, low energy atomic vibrations on the dislocation. This dislocationphonon interaction is examined for two types of interatomic potentials in a crystal with an anisotropic slip system. For realistic interatomic potentials, we find that, in the presence of an appropriate phonon, uniform motion can occur at velocities v?0.50 (in units of the speed of sound) with zero externally applied stress, or even against the direction of motion favored by such a stress.     

On the theory of nuclear heavy-ion direct transfer reactions

We review the distorted-wave approach to direct transfer reactions and draw attention to some of the shortcomings of current theories. We show that a reformulated form of the distorted-wave Born approximation (DWBA) for transfer can lead to important simplifications of the theory, which are valid for nuclear heavy-ion induced reactions at energies ? 10 MeV/nucleon. In particular, in the semiclassical limit, it leads to a new and simple formula for the transfer t-matrix which includes all the essential physics while offering several important advantages over standard “full-recoil finite-range” DWBA. One such advantage is that the new formula is more transparent in that it is amenable to interpretation and analytical manipulation. At high-energy it is shown to reduce to one earlier deduced using eikonal-DWBA.The conditions for the validity of the new theory are discussed in detail. They are shown to be generally well satisfied for small-mass transfer between heavy-ions at energies at or above those which particularly favour transfer (? 10 MeV/nucleon for transfer of valence nucleons). The restriction to small mass is not due to any recoil approximation; in fact, it is only a necessary restriction at certain energies. The theory treats recoil exactly.Consideration of the optimum dynamical conditions for transfer leads to a set of matching conditions. The presence of hitherto neglected absorption, arising from dynamical effects of poor matching, is suggested and qualitatively discussed. Conditions under which such absorption may be neglected are derived. Results of numerical calculations are presented showing that the theory is capable of good agreement with standard full-recoil finite-range DWBA, and that it is capable of giving at least as good an account of experimental data for nucleon-transfer between heavy-ions at energies ～10 MeV/nucleon.     

Molecular recognition. Self-assembly of molecular trigonal prisms and their host-guest adducts

Two supramolecular trigonal prisms, each bearing three molecular clefts are shown to form 1:6 and 1:7 host-guest complexes with 9-methylanthracene and one of the prisms forms a 1:2 host-guest complex with a tritopic tri-anthracene guest that registers with the recognition sites of the host.     

Semiclassical treatment of quadrupole shape effects in the elastic scattering of heavy ions below the Coulomb barrier

A perturbative semiclassical approximation for the elastics-matrix is used to derive simple and accurate formulae describing the effects of a nuclear quadrupole deformation on the elastic scattering of aligned nuclei. Expressions are derived for the second rank tensor components of the analysing power, the ratios of which turn out to be simple trigonometric functions of the scattering angle in agreement with experimental observations. The approximations are discussed in some detail and higher order corrections are derived. In an appendix we derive a semiclassical first-order perturbation formula describing the effect of a non-central complex perturbation in the presence of a non-perturbatively treated central term. Our formula is in disagreement with some earlier published formulae which fail to treat the real part of the perturbation correctly.     

Optically non-linear organic materials

A large number of non-linear organic materials have been investigated by second-harmonic generation (SHG) in powders. The materials studied include several urea derivatives, sterically perturbed anilines and pyridines, and substituted stilbenes. Several compounds have been found with both a very large second-order non-linearity and a high optical damage threshold. Many compounds, even though known to possess large molecular hyperpolarizabilities, showed no detectable SHG, indicating a centrosymmetric crystal point group. The results are interpreted in terms of bond configuration, charge transfer and crystal structure. The use of good non-linear organic materials in integrated non-linear optics is discussed.     

Isolation of the resonant component in acoustic scattering from fluid-loaded cylindrical shells

For the problem of scattering of a plane acoustic wave by a cylindrical elastic shell immersed in a fluid, we demonstrate that a recently proposed “intermediate background” formalism serves to separate the resonant component from the non-resonant background in the scattering amplitude. Numerical calculations are performed for the case of an air-filled aluminium shell in water.     

Partitioning the loss in vancomycin binding affinity for D-Ala-D-Lac into lost H-bond and repulsive lone pair contributions

The binding affinity of 4, which incorporates a methylene (CH2) in place of the key linking amide of Ac2-l-Lys-d-Ala-d-Ala, for vancomycin was compared with that of Ac2-l-Lys-d-Ala-d-Ala (3) and Ac2-l-Lys-d-Ala-d-Lac (5). The vancomycin affinity for 4 was approximately 10-fold less than that of 3, but 100-fold greater than that of 5. This suggests that the reduced binding affinity of 5 (4.1 kcal/mol) may be attributed to both the loss of a key H-bond (1.5 kcal/mol) and a destabilizing lone pair/lone pair electrostatic interaction introduced with the ester oxygen of 5 (2.6 kcal/mol) with the latter, not the H-bond, being responsible for the largest share of the 1000-fold reduction.