Semiclassical nonadiabatic dynamics based on quantum trajectories for the O(3P,1D) + H2 system

The O(3P,1D) + H2 --> OH + H reaction is studied using trajectory dynamics within the approximate quantum potential approach. Calculations of the wave-packet reaction probabilities are performed for four coupled electronic states for total angular momentum J = 0 using a mixed coordinate/polar representation of the wave function. Semiclassical dynamics is based on a single set of trajectories evolving on an effective potential-energy surface and in the presence of the approximate quantum potential. Population functions associated with each trajectory are computed for each electronic state. The effective surface is a linear combination of the electronic states with the contributions of individual components defined by their time-dependent average populations. The wave-packet reaction probabilities are in good agreement with the quantum-mechanical results. Intersystem crossing is found to have negligible effect on reaction probabilities summed over final electronic states.     

The multi-functional aspect of scanning holographic microscopy: a review(Invited Paper)

Recent developments in scanning holographic microscopy that offer the prospects of new quantitative tools and imaging modalities in bio, micro, and nano sciences are reviewed. The versatility of the method is emphasized. Scanning holography can operate in an incoherent mode for fluorescence imaging, in a coherent mode for quantitative phase imaging, or in a tomographic mode for axial sectioning and rejection of the out-of-focus haze. Possible applications are illustrated with examples, and future prospects ...     

6‐31G* basis set for third‐row atoms

Medium basis sets based upon contractions of Gaussian primitives are developed for the third‐row elements Ga through Kr. The basis functions generalize the 6‐31G and 6‐31G* sets commonly used for atoms up to Ar. A reexamination of the 6‐31G* basis set for K and Ca developed earlier leads to the inclusion of 3d orbitals into the valence space for these atoms. Now the 6‐31G basis for the whole third‐row K through Kr has six primitive Gaussians for 1s, 2s, 2p, 3s, and 3p orbitals, and a split‐valence pair of three and one primitives for valence orbitals, which are 4s, 4p, and 3d. The nature of the polarization functions for third‐row atoms is reexamined as well. The polarization functions for K, Ca, and Ga through Kr are single set of Cartesian d‐type primitives. The polarization functions for transition metals are defined to be a single 7f set of uncontracted primitives. Comparison with experimental data shows good agreement with bond lengths and angles for representative vapor‐phase metal complexes. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 976–984, 2001     

Primitive Illumination Systems for Families of Convex Bodies in the Plane

Let F= {C₁,C₂,...,C} be a family of ndisjoint convex bodies in the plane. We say that a set Vof exterior light sources illuminates F, if for every boundary point of any member of Fthere is a point in Vsuch that is visible from ,i.e. the open line segment joining and is disjoint from F. An illumination system Vis called primitive if no proper subset of Villuminates F. Let p_max(F) denote the maximum number of points forming a primitive illumination system for F, and letp_max(n) denote the minimum of F) taken over all families Fconsisting of ndisjoint convex bodies in the plane. The aim of this paper is to investigate the quantities p_max(F) and p_max(n).     

Lithium atom spin density from the Hiller-Sucher-Feinberg identity

Summary The electronic spin density, which determines the observed Fermi contact hyperfine splitting, is usually represented by a delta function operator at the nucleus. Approximate wavefunctions determined by overall energetic considerations may show large errors for such a highly localized property. Hiller, Sucher, and Feinberg (HSF) have shown that the delta function operator can be replaced by a global operator. The possibility that this may lead to an improved method for calculation of the spin density is examined for the ground and first excited states of the lithium atom. Particular attention is given to simple spin polarization wavefunctions that provide the leading contributions to the spin density. It is found that the delta function and HSF formulations give very nearly the same results when the wavefunctions are determined by essentially exact numerical methods. However, the HSF approach shows clear advantages in calculations carried out with finite Slater or contracted Gaussian type basis sets.     

Catalytic properties of nanostructured Pd–Ag catalysts in the liquid-phase hydrogenation of terminal and internal alkynes

A comparative catalytic study of Pd–Ag bimetallic catalysts and the commercial Lindlar catalyst (Pd–Pb/CaCO₃) has been carried out in the hydrogenation of phenylacetylene (PA) and diphenylacetylene (DPA). The Pd–Ag catalysts have been prepared using the heterobimetallic complex PdAg₂(OAc)₄(HOAc)₄ supported on MgAl₂O₄ and aluminas (α-Al₂O₃ and γ-Al₂O₃). Physicochemical studies have demonstrated that the reduction of supported Pd–Ag complex with hydrogen results in homogeneous Pd–Ag nanoparticles. Equal in selectivity to the Lindlar catalyst, the Pd–Ag catalysts are more active in DPA hydrogenation. The synthesized Pd–Ag catalysts are active and selective in PA hydrogenation as well, but the unfavorable ratio of the rates of the first and second stages of the process makes it difficult to kinetically control the reaction. The most promising results have been obtained for the Pd–Ag₂/α-Al₂O₃ catalyst. Although this catalyst is less active, it is very selective and allows efficient kinetic control of the process to be carried out owing to the fact that, with this catalyst, the rate of hydrogenation of the resulting styrene is much lower than the rate of hydrogenation of the initial PA.     

The definition of core electrons

The traditional separation of electrons in molecules into core and valence types is often based on molecular orbital energies. This method is known to lead in some cases to large relative errors in correlated calculations. Instead, we propose a method based on the definition of molecular core character using separation of basis functions into core and valence types. This gives size-consistency to separation of electrons in molecules into core and valence types.