A recipe for designing molecules with ever-increasing electron affinities

Halogens possess among the highest electron affinities of elements in the periodic table. Superhalogen molecules with electron affinities higher than those of halogen atoms have been known to form when a metal atom is surrounded with halogen atoms. Recently, it was discovered that a new class of molecules called hyperhalogens with electron affinities higher than those of superhalogens can form when the latter serve as the building block. By use of density functional theory and B3LYP hybrid exchange-correlation functional we show that molecules with electron affinities even higher can be formed by using hyperhalogens as building blocks. We demonstrate this by using Na and Li as metal atoms and F, BF(4), and Na(BF(4))(2) as halogen, superhalogen, and hyperhalogen building blocks. The predicted electron affinities of Na[Na(BF(4))(2)](2) and Li[Li(BF(4))(2)](2) are 9.18 and 9.01 eV, which are, respectively, 0.85 and 0.5 eV higher than those of their hyperhalogen [Na(BF(4))(2) and Li(BF(4))(2)] counterparts.     

Stability and spectroscopic properties of singly and doubly charged anions

Using density functional theory and hybrid B3LYP exchange-correlation energy functional we have studied the structure, stability, and spectroscopic properties of singly and doubly charged anions composed of simple metal atoms (Na, Mg, Al) decorated with halogens such as Cl and pseudohalogens such as CN. Since pseudohalogens mimic the chemistry of halogen atoms, our objective is to see if pseudohalogens can also form superhalogens much as halogens do and if the critical size for a doubly charged anion depends upon the ligand. The electron affinities of MCl(n) (M = Na, Mg, Al) exceed the value of Cl for n ≥ (k + 1), where k is the normal valence of the metal atom. However, for M(CN)(n) complexes this is only true when n = k + 1. In addition, while the electron affinities and vertical detachment energies of MCl(n) complexes are close to each other, they are markedly different when Cl is replaced by pseudohalogen, CN. The origin of these anomalous results is found to be due to the large binding energy of cyanogen, (NCCN) molecule. Because of the tendency of CN molecules to dimerize, the ground state geometries of the neutral and anionic M(CN)(n) complexes are very different when their number exceed the normal valence of the metal atom. While our calculations support the conclusion of Skurski and co-workers that pseudohalogens can form the building blocks of superhalogens, we show that there is a limitation on the number of CN moieties where this is true. Equally important, we find large differences between the ground state geometries of the neutral and anionic M(CN)(n) complexes for n ≥ (k + 2) which could play an important role in interpreting future experimental data on M(CN)(n) complexes. This is because the electron affinity defined as the energy difference between the ground states of the anion and neutral can be very different from the adiabatic detachment energy defined as the energy difference between the ground state of the anion and its structurally similar neutral isomer.     

The Role of Interface on the Properties of Cluster Assemblies

Atomic clusters characterized by finite size, low dimensionality, and reduced coordination number exhibit many novel properties that are very different from their bulk. As these clusters are assembled, their properties can be significantly altered due to the interaction of these clusters with each other as well as with their support. This paper provides a brief review of the cluster properties that are affected when clusters are deposited on metallic or organic substrates, isolated in matrices or in zeolite cages, coated with acetate ligands, or simply allowed to self-assemble without the presence of any reactive species. It is shown that the interface between the clusters and their support can play an important role on the properties of clusters as their unique characteristics do.     

Closo‐alanes (Al4H4, AlnHn+2, 4 ≤ n ≤ 8): A New Chapter in Aluminum Hydride Chemistry.

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Chemical Composition and Biological Activity of Essential Oil of Phoebe wightii

Chemistry of Natural Compounds -     

Lie-group theoretic method for analyzing interaction of discontinuous waves in a relaxing gas

A Lie group of transformations method is used to establish self-similar solutions to the problem of shock wave propagation through a relaxing gas and its interaction with the weak discontinuity wave. The forms of the equilibrium value of the vibrational energy and the relaxation time, varying with the density and pressure are determined for which the system admits self-similar solutions. A particular solution to the problem has been found out and used to study the effects of specific heat ratio and ambient density exponent on the flow parameters. The coefficients of amplitudes of reflected and transmitted waves after the interaction are determined.     

A quark model study of semileptonic baryon decays in the electronic decay modes

A relativistic quark model based on Dirac equation with the independent-quark confining potential of the form (1 +γ ⁰)[a ln(r/b)] is used to compute the weak electric and magnetic form factors for semileptonic baryonic decays in the electronic decay modes. The values obtained for (g ₂/g ₁) agree with the non relativistic results and those for (f ₂/f ₁) agree with the MIT bag model values of Donoghue and Holstein. The SU(3) symmetry breaking does not generate appreciable departures in (f ₂/f ₁) values from corresponding Cabibbo values.     

Distribution of electric field gradients around impurities in aluminum

The electric field gradients caused by a vacancy, Mg, Ga, In, Si, Ge and Sn impurities at several near-neighbor sites in Al hosts have been calculated. The theory takes into account the contribution from the conduction electron screening cloud and the lattice strain caused by the impurities. The perturbed core as well as conduction electron densities around the impurities are calculated selfconsistently using the density functional theory. Assuming that the charge distribution around the impurity is spherically symmetric, an exact expression, valid at all distances, is derived for the conduction electron contribution to the electric field gradient. While this result is substantially different from those using the conventional asymptotic or pre-asymptotic expressions, it is found to be entirely inadequate in explaining the observed asymmetry and magnitude of the electric field gradient distribution in cubic metal alloys. The contribution due to the lattice strain is calculated using the point-ion model and a new analytic form for the elastic strain tensor. The combined strain and charge screening effect provides a satisfactory agreement between calculated and experimental electric field gradients. The difficulties standing in the way of an overall quantitative understanding of the electric field gradient in cubic metal alloys are discussed. The subsequent stages of improvement in both theory and experiment that can result in a better understanding of the problem are pointed out.