The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

Cosmic dust and our origins

The small solid particles in the space between the stars provide the surfaces for the production of many simple and complex molecules. Processes involving the effects of ultraviolet irradiation of the thin (hundredth micron) mantles are shown to produce a wide range of molecules and ions also seen in comets. Some of the more complex ones inferred from laboratory experiments are expected to play an important role in the origin of life. An outline of the chemical evolution of interstellar dust as observed and as studied in the laboratory is presented. Observations of comets are shown to provide substantial evidence for their being fluffy aggregates of interstellar dust as it was in the protosolar nebula, i.e. the interstellar cloud which collapsed to form the solar system. The theory that comets may have brought the progenitors of life to the earth is summarized.     

Radial and angular correlation in heliumlike ions

In the framework of nonrelativistic variational formalism a new type of basis set is proposed, to estimate separately the effect of radial and angular correlations on the ground‐state energy for helium isoelectronic sequence H^? to Ar¹⁶⁺. Effect of radial correlation is incorporated by using multiexponential functions arising from product basis sets suitably formed out of Slater‐type one‐particle orbitals. The angular correlation can be switched on by incorporating an expansion in terms of basis involving interparticle coordinates. With a set of six‐term Slater‐type one‐particle basis and five‐term interparticle expansion, the ground‐state energy of helium is estimated as ?2.9037236 (a.u.) compared with the multiterm variational estimates ?2.9037244 (a.u.) due to Pekeris and Thakkar and Smith and Drake. Matrix elements of different operators in the ground state have been calculated and found to be in good agreement with available accurate results. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003     

Structure and Structural Nonrigidity of Tetrachlorodibenzo-p-Dioxin Radical Cations

Ab initio calculations showed that the tetrachlorodibenzo-para-dioxin radical cations (TCDD RCs) with a planar structure have two steady states with asymmetric dioxin cycles. The activation barriers between these states are up to 2 kcal/mole, so that the RCs may be regarded as being structurally nonrigid within the dioxin cycle. The 2,3,7,8-TCDD RC is more stable than the 1,4,6,9-TCDD RC, the energy difference being 5.2 kcal/mole. The adiabatic ionization potential of 2,3,7,8-TCDD (7.54 eV) is 0.1 eV smaller than the corresponding potential of 1,4,6,9-TCDD. These factors account for the increased hemoproteide affinity and hence increased biological activity of 2,3,7,8-TCDD.     

Propagation of mesons in asymmetric nuclear matter in a density-dependent coupling model

We study the propagation of the light mesons σ,ω,ρ, and a₀(980) in dense hadronic matter in an extended derivative scalar coupling model. Within the scheme proposed it is possible to unambiguously define effective density-dependent couplings at the Lagrangian level. We first apply the model to study asymmetric nuclear matter with fixed isospin asymmetry, and then we pay particular attention to hypermatter in β-equilibrium. The equation of state and the potential contribution to the symmetry coefficient arising from the mean-field approximation are investigated. Received: 16 October 2001 / Accepted: 10 January 2002     

Structure of enantiopure and racemic alanine adlayers on Cu(1 1 0)

Plane wave density functional theory has been employed to analyze the structure of alanine adlayers on the Cu(1 1 0) surface. Alanine forms (3 × 2) adlayers on Cu(1 1 0) that are closely related to the structures of glycine on the same surface. There is essentially no energy difference between the most stable racemic and enantiopure alanine adlayers. This observation implies that adsorption of racemic alanine on Cu(1 1 0) will result in a pseudoracemate adlayer.     

Organocatalysis: quantum chemical modeling of nucleophilic addition to α,β‐unsaturated carbonyl compounds

One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd.     

Ultrathin Fe film on Cu(0 0 1): Exchange splitting of image states from first principles

The theoretical investigation of the image states in front of an ultrathin iron film grown on copper has been performed by means of the embedding method and a recently developed procedure for the inclusion of the image potential tail in a first principle calculation. From the electronic response to an applied electric field, the image plane position has been evaluated. This also allows one to obtain useful information about the spin dependent screening properties of the system. Exchange splitting, effective mass, and lifetime of such surface states result in good agreement with recently performed two-photon photoemission experiments [see A.B. Schmidt, M. Pickel, M. Wiemhöfer, M. Donath, M. Weinelt, Phys. Rev. Lett. 95 (2005) 107402].     

Isosteres of peptides: boron analogs as dipolar forms of α‐amino acids – a theoretical study

Modification of peptides to produce peptidomimetics is of great interest, with the aim of designing potent, selective, and metabolically stable analogs having certain conformational properties. Organoboranes have been reported in the literature with a wide range of therapeutic applications. One of the therapeutically important class of molecules is amine‐carboxyboranes derived from amino acids by replacement of the Cα atom of an amino acid/peptide by boron. The conformational preferences of these peptides, with respect to backbone ω, ?, and ψ torsion angles, have been investigated by theoretical calculations. The amide bond in these molecules has the same geometry in the ground and transition states as the natural peptides. However, the boron isosteres of glycine and alanine peptides are less structured than their natural derivatives, but are distinguished by structures with a positive value for the ? angle, which is normally disfavored for natural peptides. This property could be used to build peptides with a geometry not usually seen in natural peptides. Copyright © 2007 John Wiley & Sons, Ltd.     

Ab-initio simulation of elastic constants for some ceramic materials

Athermal elasticity for some ceramic materials (α-Al₂O₃, SiC (α and β phases), TiO₂ (rutile and anatase), hexagonal AlN and TiB₂, cubic BN and CaF₂, and monoclinic ZrO₂) have been investigated via density functional theory. Energy-volume equation-of-state computations to obtain the zero pressure equilibrium volume and bulk modulus as well as computations of the full elastic constant tensor of these ceramics at the experimental zero pressure volume have been performed. The present results for the single crystal elasticity are in good agreement with experiments both for the aggregate properties (bulk and shear modulus) and the elastic anisotropy. In contrast, a considerable discrepancy for the zero pressure bulk modulus of some ceramics evaluated from the energy-volume fit to the computational zero pressure volume has been observed.