Electronic properties of a methane-water solution

Electronic properties of a methane-water solution were investigated by a sequential quantum mechanical/molecular dynamics approach. Upon hydration methane acquires an induced dipole moment of similar to 0.5 +/- 0.2 D. This is related to polarisation effects and to weak methane-water hydrogen bond interactions. From gas phase to solution, the first vertical excitation and ionisation energies of methane are red-shifted by 0.45 +/- 0.25 and 0.87 +/- 0.40 eV, respectively. We also report results for the dynamic polarisability of methane in water. In comparison with water, no difference was found for the average monomeric dipole moment of water molecules in close interaction with methane. (c) 2011 Elsevier B.V. All rights reserved.

Polarization and solvatochromic shift of ortho-betaine in water

Betaine dyes are known to show very large transition energy shifts in different solvents. The ortho-betaine molecule - a simple two-ring prototype of the E-T(30) Reichardt dye - has been investigated theoretically from a combined statistical and quantum mechanics approach. Using sequential Monte Carlo (MC) simulations and MP2/cc-pVDZ calculations the in-water dipole moment of ortho-betaine is obtained as 12.30 +/- 0.05 D. This result shows a considerable increase of 75% compared to the in-vacuum dipole moment. For comparison, the use of a polarizable continuum model using the same MP2/cc-pVDZ leads to an in-water dipole moment of 11.6 D, in good agreement. This large polarization is incorporated in the classical potential for another MC simulation to generate solute-solvent configurations and to obtain the contribution of the polarization effect in the solvatochromic shift. Using statistically uncorrelated configurations and supermolecular INDO/CIS calculations, including the solute and, explicitly, 230 solvent water molecules, the statistically converged calculated shift is obtained here as 6360 cm(-1), in good agreement with the experimental result of 7550 cm(-1). (c) 2007 Elsevier B.V. All rights reserved.

Calculations of vibrational frequencies, Raman activities and degrees of depolarization for complexes involving water, methanol and ethanol

Raman activities and degrees of depolarization are reported for 14 complexes involving methanol, ethanol and water using the MP2/aug-cc-pVDZ model. For ethanol both trans and gauche isomers are considered. The red-shifts of the OH stretching and the blue shifts of the bending tau(CO-OH) mode were analyzed for the proton-donor molecules upon hydrogen bond. The shift of the nu(CO) stretching mode of the alcohol molecules are also analyzed and found to be specific giving characterization of the amphoteric relation, being positive for the proton-acceptor and negative for the proton-donor molecule. (c) 2008 Elsevier B.V. All rights reserved.

Conformational behavior of different possible ways of oligoglycine formation in a solvent-free environment

The possible ways for glycine oligopeptide formation in gas phase, both in the extended P-strand like conformation and folded 2(7)-ribbon like conformations are analyzed using quantum chemical calculations. We focus on the sequential formation of peptide bond through upgradation of the immediate lower order molecule and observe the consequences in other related processes like oligoglycine formation through simultaneous peptide linkage of n glycine monomers and interchange of molecular conformation through peptide linkage. A comparison is made between the structures and binding energies obtained for both conformers. All binding energies are increased by the zero-point energy contribution. The role of electron correlation effects is briefly analyzed. The folded 2(7)-ribbon-like conformations in vacuo are found to be more stable in comparison to the extended structure. (c) 2007 Elsevier B.V. All rights reserved.

Renormalization of the S parameter in holographic models of electroweak symmetry breaking

We show that the S parameter is not finite in theories of electroweak symmetry breaking in a slice of anti-de Sitter five-dimensional space, with the light fermions localized in the ultraviolet. We compute the one-loop contributions to S from the Higgs sector and show that they are logarithmically dependent on the cutoff of the theory. We discuss the renormalization of S, as well as the implications for bounds from electroweak precision measurements on these models. We argue that, although in principle the choice of renormalization condition could eliminate the S parameter constraint, a more consistent condition would still result in a large and positive S. On the other hand, we show that the dependence on the Higgs mass in S can be entirely eliminated by the renormalization procedure, making it impossible in these theories to extract a Higgs mass bound from electroweak precision constraints.

Sub-barrier fusion of two-neutron halo nuclei

The tunneling of composite systems, where breakup may occur during the barrier penetration process, is considered in connection with the fusion of halo-like radioactive, neutron- and proton-rich nuclei, on heavy targets. The large amount of recent and new data clearly indicates that breakup hinders the fusion at energies near and below the Coulomb barrier. However, clear evidence for enhancement due to halo properties seems to over ride the breakup hindrance at lower energies, owing, to a large extent, to the extended matter density distribution. In particular we report here that at sub-barrier energies the fusion cross section of the Borromean two-neutron halo nucleus (6)He with the actinide nucleus (238)U is significantly enhanced as compared to the fusion of a similar projectile with no halo. This conclusion differs from that of the original work, where it was claimed that no such enhancement ensues. This sub-barrier fusion enhancement is also observed in the (6)He + (209)Bi system. (C) 2010 Elsevier B.V. All rights reserved.

Transition metal atoms encapsulated in adamantane molecules

We performed a first principles total energy investigation on the structural, electronic, and magnetic properties of 3d-transition metal-encapsulated adamantane molecules (TM@C(10)H(16). with TM = Cr, Mn, Fe, Co, and Ni). We find that the C-C interactions are strong enough to maintain the molecular rigidity upon TM incorporation, although outward relaxations and formation energies are large. We built a microscopic model that explains the electronic structure of those molecules. (C) 2011 Elsevier B.V. All rights reserved.

Electronic and magnetic properties of Ti and Fe on graphene

The structural, electronic and magnetic properties of Fe and Ti atomic wires and the complete covering when adsorbed on graphene are presented through ab initio calculations based on density functional theory. The most stable configurations are investigated for Fe and Ti in different concentrations adsorbed on the graphene surface, and the corresponding binding energies are calculated. The results show a tendency of the Ti atoms to cover uniformly the graphene surface, whereas the Fe atoms form clusters. The adsorption of the transition metal on the graphene surface changes significantly the electronic density of states near the graphene Fermi region. In all arrangements studied, a charge transfer is observed from the adsorbed species to the graphene surface due to the high hybridizations between the systems.

SiO(2) in density functional theory and beyond

We present the first-principle electronic structure calculation on an amorphous material including many-body corrections within the GW approximation. We show that the inclusion of the local field effects in the exchange-correlation potential is crucial to quantitatively describe amorphous systems and defect states. We show that the mobility gap of amorphous silica coincides with the band gap of quartz, contrary to the traditional picture and the densityfunctional theory results. (C) 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Ab initio study of SO2 molecules interacting with pristine and transition metal covered fullerenes as a possible route for nanofilters

In this work, a systematic study of SO2 molecules interacting with pristine and transition metal (TM) covered C-60 is presented by means of first principles calculations. It is observed that the SO2 molecule interacts weakly with the pristine C-60 fullerene, although the resulting interaction is largely increased when the C-60 structure is covered with Fe, Mn, or Ti atoms and the SO2 Molecules are bounded through the TM atoms. The number of bounded SO2 molecules per TM atoms, in addition to the elevated binding energies per molecules, allows us to conclude that such composites can be used as a template for efficient devices to remove SO2 molecules or, alternatively, as SO2 gas sensor.

Hydrogen adsorption on boron doped graphene: an ab initio study

(i) The electronic and structural properties of boron doped graphene sheets, and (ii) the chemisorption processes of hydrogen adatoms on the boron doped graphene sheets have been examined by ab initio total energy calculations. In (i) we find that the structural deformations are very localized around the boron substitutional sites, and in accordance with previous studies (Endo et al 2001 J. Appl. Phys. 90 5670) there is an increase of the electronic density of states near the Fermi level. Our simulated scanning tunneling microscope (STM) images, for occupied states, indicate the formation of bright (triangular) spots lying on the substitutional boron (center) and nearest-neighbor carbon (edge) sites. Those STM images are attributed to the increase of the density of states within an energy interval of 0.5 eV below the Fermi level. For a boron concentration of similar to 2.4%, we find that two boron atoms lying on the opposite sites of the same hexagonal ring (B1-B2 configuration) represents the energetically most stable configuration, which is in contrast with previous theoretical findings. Having determined the energetically most stable configuration for substitutional boron atoms on graphene sheets, we next considered the hydrogen adsorption process as a function of the boron concentration, (ii). Our calculated binding energies indicate that the C-H bonds are strengthened near boron substitutional sites. Indeed, the binding energy of hydrogen adatoms forming a dimer-like structure on the boron doped B1-B2 graphene sheet is higher than the binding energy of an isolated H(2) molecule. Since the formation of the H dimer-like structure may represent the initial stage of the hydrogen clustering process on graphene sheets, we can infer that the formation of H clusters is quite likely not only on clean graphene sheets, which is in consonance with previous studies (Hornekaer et al 2006 Phys. Rev. Lett. 97 186102), but also on B1-B2 boron doped graphene sheets. However, for a low concentration of boron atoms, the formation of H dimer structures is not expected to occur near a single substitutional boron site. That is, the formation (or not) of H clusters on graphene sheets can be tuned by the concentration of substitutional boron atoms.

The magnetic phase diagram of Gd(2)Sn(2)O(7)

Measurements of the magnetic susceptibility of the frustrated pyrochlore magnet Gd(2)Sn(2)O(7) have been performed at temperatures below T = 5 K and in magnetic fields up to H = 12 T. The phase boundaries determined from these measurements are mapped out in an H-T phase diagram. In this gadolinium compound, where the crystal-field splitting is small and the exchange and dipolar energy are comparable, the Zeeman energy overcomes these competing energies, resulting in at least four magnetic phase transitions below 1 K. These data are compared against those for Gd(2)Ti(2)O(7) and will, we hope, stimulate further studies.

Driving forces for the adsorption of cyclopentene on InP(001)

In this work the interaction of cyclopentene with a set of InP(001) surfaces is investigated by means of the density functional theory. We propose a simple approach for evaluating the surface strain and based on it we have found a linear relation between bond and strain energies and the adsorption energy. Our results also indicate that the higher the bond energy, the more disperse the charge distribution is around the adsorption site associated to the high occupied state, a key feature that characterizes the adsorption process. Different adsorption coverages are used to evaluate the proposed equation. Our results suggest that the proposed approach might be extended to other systems where the interaction of the semiconductor surface and the molecule is restricted to first neighbor sites. (C) 2011 Elsevier B.V. All rights reserved.

Energetics and stability of vacancies in carbon nanotubes

In this work we present ab initio calculations of the formation energies and stability of different types of multi-vacancies in carbon nanotubes. We demonstrate that, as in the case of graphene, the reconstruction of the defects has drastic effects on the energetics of the tubes. In particular, the formation of pentagons eliminates the dangling bonds thus lowering the formation energy. This competition leads to vacancies having an even number of carbon atoms removed to be more stable. Finally the appearance of magic numbers indicating more stable defects can be represented by a model for the formation energies that is based on the number of dangling bonds of the unreconstructed system, the pentagons and the relaxation of the final form of the defect formed after the relaxation. (C) 2011 Elsevier Ltd. All rights reserved.

Crystal engineering using functionalized adamantane

We performed a first-principles investigation on the structural, electronic and optical properties of crystals made of chemically functionalized adamantane molecules. Several molecular building blocks, formed by boron and nitrogen substitutional functionalizations, were considered to build zinc blende and wurtzite crystals, and the resulting structures presented large bulk moduli and cohesive energies, wide and direct bandgaps, and low dielectric constants (low-kappa materials). Those properties provide stability for such structures up to room temperature, superior to those of typical molecular crystals. This indicates a possible road map for crystal engineering using functionalized diamondoids, with potential applications ranging from space filling between conducting wires in nanodevices to nano-electromechanical systems.