Gas-phase solvolysis type reactions of SiCl3+ cations

Gas-phase SiCl3+ ions undergo sequential solvolysis type reactions with water, methanol, ammonia, methylamine and propylene. Studies carried out in a Fourier Transform mass spectrometer reveal that these reactions are facile at 10-8 Torr and give rise to substituted chlorosilyl cations. Ab initio and DFT calculations reveal that these reactions proceed by addition of the silyl cation to the oxygen or nitrogen lone pair followed by a 1,3-H migration in the transition state. These transition states are calculated to lie below the energy of the reactants. By comparison, hydrolysis of gaseous CCl3+ is calculated to involve a substantial positive energy barrier.

A theoretical study of the tautomerism and vibrational spectra of 4,5-diamine-2,6-dimercaptopyrimidine

The 4,5-diamine-2,6-dimercaptopyrimidine (DADMcP) compound is an interesting multifunctional species exhibiting a rather complex tautomerism, encompassing nine tautomeric forms. Investigation of tautomerism in this compound has been carried out by means of FTIR spectroscopy, in association with ab-initio HF/SCF and DFT calculations. According to this study three tautomers are energetically favored; the thione form being the most stable one. The theoretical vibrational spectra of such tautomeric forms have been successfully simulated by means of DFT calculations, allowing the elucidation and assignment of the complex composition of the vibrational bands observed for the mixture of isomers.

Interleukin-22 forms dimers that are recognized by two interleukin-22R1 receptor chains

Interleukin-22 (IL-22) is a class 2 cytokine whose primary structure is similar to that of interleukin 10 (IL-10) and interferon-gamma (IFN-gamma). IL-22 induction during acute phase immune response indicates its involvement in mechanisms of inflammation. Structurally different from IL-10 and a number of other members of IL-10 family, which form intertwined inseparable V-shaped dimers of two identical polypeptide chains, a single polypeptide chain of IL-22 folds on itself in a relatively globular structure. Here we present evidence, based on native gel electrophoresis, glutaraldehyde cross-linking, dynamic light scattering, and small angle x-ray scattering experiments, that human IL-22 forms dimers and tetramers in solution under protein concentrations assessable by these experiments. Unexpectedly, low-resolution molecular shape of IL-22 dimers is strikingly similar to that of IL-10 and other intertwined cytokine dimeric forms. Furthermore, we determine an ab initio molecular shape of the IL-22/IL-22R1 complex which reveals the V-shaped IL-22 dimer interacting with two cognate IL-22R1 molecules. Based on this collective evidence, we argue that dimerization might be a common mechanism of all class 2 cytokines for the molecular recognition with their respective membrane receptor. We also speculate that the IL-22 tetramer formation could represent a way to store the cytokine in nonactive form at high concentrations that could be readily converted into functionally active monomers and dimers upon interaction with the cognate cellular receptors.

Anomalous thermodynamic properties in ferropericlase throughout its spin crossover transition

The thermodynamics properties of ferropericlase (Mg(1-x)Fe(x)O where x=0.1875) (Fp) throughout its spin crossover were investigated by first principles. Fp was treated as an ideal solid solution of pure high-spin and low-spin states. The Gibbs free energies of the pure states were addressed using the LDA+U method. A vibrational virtual-crystal model was developed to address the vibrational properties of the pure spin cases and used in conjunction with quasiharmonic theory to compute their vibrational free energies. The thermodynamics properties of Fp display significant anomalies that should be typical of spin crossover systems in general. In Fp, in particular, they are fundamental for understanding the state of earth's interior, where the pressure and temperature conditions of the crossover are realized.

Electronic properties and hyperfine fields of nickel-related complexes in diamond

We carried out a first-principles investigation on the microscopic properties of nickel-related defect centers in diamond. Several configurations, involving substitutional and interstitial nickel impurities, have been considered either in isolated configurations or forming complexes with other defects, such as vacancies and boron and nitrogen dopants. The results, in terms of spin, symmetry, and hyperfine fields, were compared with the available experimental data on electrically active centers in synthetic diamond. Several microscopic models, previously proposed to explain those data, have been confirmed by this investigation, while some models could be discarded. We also provided insights into the microscopic structure of several of those centers.

Piezomagnetic behavior of Co-doped ZnO nanoribbons

Using ab initio total energy calculations, we show that bilayer systems of ZnO nanoribbons, (ZnO)(2)NR, doped with Co atoms exhibit a piezomagnetic behavior. We find the formation of energetically stable zigzag chains of Co atoms along the edge sites of (ZnO)(2)NR's, Co(Zn(chain))-(ZnO)(2)NR. At the ground state, the antiferromagnetic and the ferromagnetic states are very close in energy, whereas upon longitudinal stretch, parallel to the nanoribbon growth direction, it becomes ferromagnetic. Further electronic structure calculations indicate that not only the magnetic state but also the electronic structure of CoZn(chain)-(ZnO)(2)NR can be tuned by the mechanical stretch. In this case, we find that stretched NR's exhibit dispersive unpaired electronic states within the (ZnO)(2)NR band gap.

Formation of atomic carbon chains from graphene nanoribbons

The formation of one-dimensional carbon chains from graphene nanoribbons is investigated using ab initio molecular dynamics. We show under what conditions it is possible to obtain a linear atomic chain via pulling of the graphene nanoribbons. The presence of dimers composed of two-coordinated carbon atoms at the edge of the ribbons is necessary for the formation of the linear chains, otherwise there is simply the full rupture of the structure. The presence of Stone-Wales defects close to these dimers may lead to the formation of longer chains. The local atomic configuration of the suspended atoms indicates the formation of single and triple bonds, which is a characteristic of polyynes.

Splitting of the zero-energy edge states in bilayer graphene

Bilayer graphene nanoribbons with zigzag termination are studied within the tight-binding model. We also include single-site electron-electron interactions via the Hubbard model within the unrestricted Hartree-Fock approach. We show that either the interactions between the outermost edge atoms or the presence of a magnetic order can cause a splitting of the zero-energy edge states. Two kinds of edge alignments are considered. For one kind of edge alignment (?) the system is nonmagnetic unless the Hubbard parameter U becomes greater than a critical value Uc. For the other kind of edge alignment (?) the system is magnetic for any U>0. Our results agree very well with ab initio density functional theory calculations.

Anomalous lattice parameter of magnetic semiconductor alloys

The addition of transition metals to III-V semiconductors radically changes their electronic, magnetic, and structural properties. We show by ab initio calculations that in contrast to the conventional semiconductor alloys, the lattice parameter in magnetic semiconductor alloys, including those with diluted concentration, strongly deviates from Vegard's law. We find a direct correlation between the magnetic moment and the anion-transition metal bond lengths and derive a simple and general formula that determines the lattice parameter of a particular magnetic semiconductor by considering both the composition and magnetic moment. This dependence can explain some experimentally observed anomalies and stimulate other kind of investigations.

Electronic, structural, and transport properties of Ni-doped graphene nanoribbons

We have investigated the electronic and transport properties of zigzag Ni-adsorbed graphene nanoribbons (Ni/GNRs) using ab initio calculations. We find that the Ni adatoms lying along the edge of zigzag GNRs represent the energetically most stable configuration, with an energy difference of approximately 0.3 eV when compared to the adsorption in the middle of the ribbon. The carbon atoms at the ribbon edges still present nonzero magnetic moments as in the pristine GNR even though there is a quenching by a factor of almost five in the value of the local magnetic moments at the C atoms bonded to the Ni. This quenching decays relatively fast and at approximately 9 A from the Ni adsorption site the magnetic moments have already values close to the pristine ribbon. At the opposite edge and at the central carbon atoms the changes in the magnetic moments are negligible. The energetic preference for the antiparallel alignment between the magnetization at the opposite edges of the ribbon is still maintained upon Ni adsorption. We find many Ni d-related states within an energy window of 1 eV above and below the Fermi energy, which gives rise to a spin-dependent charge transport. These results suggest the possibility of manufacturing spin devices based on GNRs doped with Ni atoms.

Atomistic molecular dynamics study of interface formation: Al on poly(p-phenylene vinylene)

We model interface formation by metal deposition on the conjugated polymer poly-para-phenylene vinylene, studying direct aluminum and layered aluminum-calcium structures Al/PPV and Al/Ca/PPV. To do that we use classical molecular dynamics simulations, checked by ab initio density-functional theory calculations, for selected relevant configurations. We find that Al not only migrates easily into the film, with a strong charge transfer to the neighboring chains, but also promotes rearrangement of the polymer in the interfacial region to the hexagonal structure. On the other hand, our results indicate that a thin Ca layer is sufficient to protect the film and maintain a well-defined metal/polymer interface, and that also a thin Al capping layer may protect the whole from environmental degradation.

Defect-induced effects on carrier migration through one-dimensional poly(para-phenylenevinylene) chains

Defects in one-dimensional (1D) systems can be intrinsically distinct from its three-dimensional counterparts, and polymer films are good candidates for showing both extremes that are difficult to individuate in the experimental data. We study theoretically the impact of simple hydrogen and oxygen defects on the electron transport properties of one-dimensional poly(para-phenylenevinylene) chains through a multiscale technique, starting from classical structural simulations for crystalline films to extensive ab initio calculations within density functional theory for the defects in single crystalline-constrained chains. The most disruptive effect on carrier transport comes from conjugation breaking imposed by the overcoordination of a carbon atom in the vinyl group independently from the chemical nature of the defect. The particular case of the [C=O] (keto-defect) shows in addition unexpected electron-hole separation, suggesting that the experimentally detected photoluminescence bleaching and photoconductivity enhancement could be due to exciton dissociation caused by the 1D characteristics of the defect.

Adiabatic intramolecular movements for water systems

An effective treatment of the intramolecular degrees of freedom is presented for water, where these modes are decoupled from the intermolecular ones, ""adiabatically"" allowing these coordinates to be positioned at their local minimum of the potential energy surface. We perform ab initio Monte Carlo simulations with the configurational energies obtained via density functional theory. We study a water dimer as a prototype system, and even in this simple case the intramolecular relaxations are very important to properly describe properties such as the dipole moment. We show that rigid simulations do not correctly sample the phase space, resulting in an average dipole moment smaller than the one obtained with the adiabatic model, which is closer to the experimental result. (c) 2008 American Institute of Physics.

First-principles study of the adsorption of atomic and molecular hydrogen on BC(2)N nanotubes

The adsorption of atomic and molecular hydrogen on armchair and zigzag boron carbonitride nanotubes is investigated within the ab initio density functional theory. The adsorption of atomic H on the BC(2)N nanotubes presents properties which are promising for nanoelectronic applications. Depending on the adsorption site for the H, the Fermi energy moves toward the bottom of the conduction band or toward the top of the valence band, leading the system to exhibit donor or acceptor characteristics, respectively. The H(2) molecules are physisorbed on the BC(2)N surface for both chiralities. The binding energies for the H(2) molecules are slightly dependent on the adsorption site, and they are near to the range to work as a hydrogen storage medium.

Elementary Excitations at Magnetic Surfaces and Their Spin Dependence

The elementary surface excitations are studied by spin-polarized electron energy loss spectroscopy on a prototype oxide surface [an oxygen passivated Fe(001)-p(1 x 1) surface], where the various excitations coexist. For the first time, the surface phonons and magnons are measured simultaneously and are distinguished based on their different spin nature. The dispersion relation of all excitations is probed over the entire Brillouin zone. The different phonon modes observed in our experiment are described by means of ab initio calculations.