Bond-order potentials with split-charge equilibration: application to C-, H-, and O-containing systems

A method for extending charge transfer to bond-order potentials, known as the bond-order potential/split-charge equilibration (BOP/SQE) method [P. T. Mikulski, M. T. Knippenberg, and J. A. Harrison, J. Chem. Phys. 131, 241105 (2009)], is integrated into a new bond-order potential for interactions between oxygen, carbon, and hydrogen. This reactive potential utilizes the formalism of the adaptive intermolecular reactive empirical bond-order potential [S. J. Stuart, A. B. Tutein, and J. A. Harrison, J. Chem. Phys. 112, 6472 (2000)] with additional terms for oxygen and charge interactions. This implementation of the reactive potential is able to model chemical reactions where partial charges change in gas- and condensed-phase systems containing oxygen, carbon, and hydrogen. The BOP/SQE method prevents the unrestricted growth of charges, often observed in charge equilibration methods, without adding significant computational time, because it makes use of a quantity which is calculated as part of the underlying covalent portion of the potential, namely, the bond order. The implementation of this method with the qAIREBO potential is designed to provide a tool that can be used to model dynamics in a wide range of systems without significant computational cost. To demonstrate the usefulness and flexibility of this potential, heats of formation for isolated molecules, radial distribution functions of liquids, and energies of oxygenated diamond surfaces are calculated.     

Dynamics of the sputtering of water from ice films by collisions with energetic xenon atoms

The flow of energy from the impact site of a heavy, translationally energetic xenon atom on an ice surface leads to several non-equilibrium events. The central focus of this paper is on the collision-induced desorption (sputtering) of water molecules into the gas-phase from the ice surface. Sputtering is strongly activated with respect to xenon translational energy, and a threshold for desorption was observed. To best understand these results, we discuss our findings in the context of other sputtering studies of molecular solids. The sputtering yield is quite small; differential measurements of the energy of xenon scattered from ice surfaces show that the ice efficiently accommodates the collisional energy. These results are important as they quantitatively elucidate the dynamics of such sputtering events, with implications for energetic non-equilibrium processes at interfaces.     

Interactive effects of pore size control and carbonization temperatures on supercapacitive behaviors of porous carbon/carbon nanotube composites

Porous carbon-based electrodes were prepared by carbonization with poly(vinylidene fluoride) (PVDF)/carbon nanotube (CNT) composites to further increase the specific capacitance for supercapacitors. The specific capacitance, pore size distribution, and surface area of the PVDF/CNT composites were measured, and the effect of the carbonization temperatures was examined. The electrochemical properties were examined by cyclic voltammetry, impedance spectroscopy, and galvanostatic charge-discharge performance using a two-electrode system in TEABF(4) (tetraethylammonium tetrafluoroborate)/acetonitrile as a non-aqueous electrolyte. The highest specific capacitance of ～101 Fg(-1) was obtained for the samples carbonized at 600 °C. The pore size of the samples could be controlled to below 7 nm through the carbonization process. This suggests that micropores make a significant contribution to the specific capacitance due to improved charge transfer between the pores of the electrode materials and the electrolyte.     

Lanthanide doping-facilitated growth of ultrasmall monodisperse Ba2LaF7 nanocrystals with excellent photoluminescence

Lanthanide doping not only works as sensitizer and activator, but also plays an important role to facilitate the growth of nanocrystal and to control the size, shape, and property of nanocrystals. Here, reported was the synthesis of monodisperse Ba(2)LaF(7) nanocrystals with the size of sub-10nm through a solvothermal method. We found the dopants of Ho(3+), Er(3+), or Yb(3+) facilitated the growth of Ba(2)LaF(7) nanocrystals obviously to a certain size within a shorter reaction time. Similar phenomenon can also be observed in the synthesis of LaF(3) nanocrystals. We find that Ln(3+) (e.g., Ho(3+), Er(3+), or Yb(3+)) with smaller radius can reduce the nucleation energy and lead to heterogeneous nucleation, which favors the growth of Ba(2)LaF(7) nanocrystals obviously. In addition, intense upconversion emission can be observed from Ln(3+)-doped Ba(2)LaF(7) nanocrystals under the 980 nm laser excitation, providing great potential application in biological imaging. Especially, Ba(2)LaF(7):Yb/Er (20/1 mol%) nanocrystals present more intense upconversion emission than α-NaYF(4):Yb/Er (20/1 mol%) nanocrystals under the same conditions.     

Effect of plasma etching on photoluminescence of SnO(x)/Sn nanoparticles deposited on DOPC lipid membrane

The photoluminescence characteristic of the SnO(x)/Sn nanoparticles deposited on a solid supported liquid-crystalline phospholipid (1,2-dioleoyl-sn-glycero-3-phosphocholine) membrane was probed after plasma etching the nanoparticle monolayer. It was shown that the plasma etching of the nanoparticle surface greatly altered the particle morphology and enhanced the PL effect, especially when the particle size was below 10 nm in spite of strong presence of surrounding carbon. The enhancement mainly stemmed from the growth of a new PL peak due to the additional defect states produced on the nanoparticle surface by the plasma etching. It was also shown that hydrating the SnO(x)/Sn nanoparticles similarly improved the PL response of the nanoparticles as the hydration produced an additional oxygen-rich oxide layer on the particle surface.     

Synthesis of the HCV protease inhibitor Vaniprevir (MK-7009) using ring-closing metathesis strategy

A highly efficient synthesis of Vaniprevir (MK-7009) has been accomplished in nine linear steps and 55% overall yield. The key features of this synthesis include a cost-effective synthesis of the isoindoline subunit and efficient construction of the 20-membered macrocyclic core of Vaniprevir (MK-7009) utilizing ring-closing metathesis technology. A high-performing ring-closing metathesis protocol has been achieved by simultaneous slow addition of the ruthenium catalyst (0.2 mol %) and the diene substrate at a concentration of 0.13 M.     

Evidence of enhanced conjugation in ortho-arylene ethynylenes with transition metal coordination

The effective conjugation of ortho and ortho-alt-para-arylene ethynylenes, with appropriately positioned pyridine and pyrazine heterocycles, increases upon binding to Ag(I) and Pd(II) cations. Significant bathochromic shifts in the electronic spectra, witnessed upon introduction of these metal bridges, are consistent with enhanced electron delocalization in the unsaturated backbone. Control studies suggest that this electronic behavior is attributable exclusively (in the case of Ag(I)) or partially (in the case of Pd(II)) to conformational restrictions of the conjugated backbones.     

Influence of the cation size on the framework structures and space group centricities in AMo2O5(SeO3)2 (A = Sr, Pb, and Ba)

Two new quaternary mixed-metal selenites, SrMo(2)O(5)(SeO(3))(2) and PbMo(2)O(5)(SeO(3))(2), have been synthesized as crystals and pure polycrystalline phases by standard solid-state reactions using SrMoO(4), PbO, MoO(3), and SeO(2) as reagents. The crystal structures of the reported materials have been determined by single-crystal X-ray diffraction. SrMo(2)O(5)(SeO(3))(2) and PbMo(2)O(5)(SeO(3))(2) are isostructural and crystallized in the triclinic centrosymmetric space group P1? (No. 2). The reported materials exhibit chain structures consisting of MoO(6) octahedra and asymmetric SeO(3) polyhedra. Complete characterizations including IR spectroscopy and thermal analyses for the compounds are also presented, as are dipole moment calculations. In addition, the powder second-harmonic-generating (SHG) properties of noncentrosymmetric polar BaMo(2)O(5)(SeO(3))(2) have been measured using 1064 nm radiation. Through powder SHG measurement, we are able to determine that BaMo(2)O(5)(SeO(3))(2) has a SHG efficiency of approximately 80 times that of α-SiO(2). Additional SHG measurements reveal that the material is phase-matchable (type 1). A detailed cation size effect on the symmetry and framework structure is discussed.     

Formation of the imide [Ta(NMe2)3(μ-NSiMe3)]2 through an unprecedented α-SiMe3 abstraction by an amide ligand

Ta(NMe(2))(4)[N(SiMe(3))(2)] (1) undergoes the elimination of Me(3)Si-NMe(2) (2), converting the -N(SiMe(3))(2) ligand to the ═NSiMe(3) ligand, to give the imide "Ta(NMe(2))(3)(═NSiMe(3))" (3) observed as its dimer 4. CyN═C═NCy captures 3 to yield guanidinates Ta(NMe(2))(3-n)(═NSiMe(3))[CyNC(NMe(2))NCy](n) [n = 1 (5), 2 (6)]. The kinetic study of α-SiMe(3) abstraction in 1 gives ΔH(?) = 21.3(1.0) kcal/mol and ΔS(?) = -17(2) eu.     

Synthesis and Structure of Bismuth(III)-Containing Noncentrosymmetric Phosphates, Cs(3)KBi(2)M(4)(PO(4))(6)Cl (M = Mn, Fe). Monoclinic (Cc) and Tetragonal (P4(3)) Polymorphs Templated by Chlorine-Centered Cl(Bi(2)Cs) Acentric Units

Single crystals of three new noncentrosymmetric (NCS) phosphates, α (1) and β (2) forms of Cs(3)KBi(2)Mn(4)(PO(4))(6)Cl and α-Cs(3)KBi(2)Fe(4)(PO(4))(6)Cl (3), were grown in a reactive CsCl/KCl molten-salt media. Their structures were determined by single-crystal X-ray diffraction methods showing that the α form crystallizes in the space group Cc (No. 9), which is in one of the 10 NCS polar crystal classes, m (2/m) while the β form crystallizes in P4(3) (No. 78) of another polar class, 4 (4/m). The unit cell parameters of the α form can be approximately correlated with that of the β form via the 3 × 3 orientation matrix [0.5, 0.5, 0; -0.5, 0.5, 0; 0, 0, 2 sin β]. The structures of these otherwise complicated phosphates exhibit two types of channels with circular and elliptical windows where the Cl-centered Cl(Bi(2)Cs) acentric unit is located. The neighboring acentric units are arranged in a parallel fashion in the α form, resulting in the monoclinic (Cc) lattice, but "antiparallel" in the β form, thus giving the tetragonal (P4(3)) unit cell. 1-3 feature the compatible M-O-P unit that contains four crystallographically independent MO(x) (x = 4, 5) polyhedra, which are connected to the Cl(Bi(2)Cs) acentric unit through one short and one long M(II)···Cl bond. The compositions of 1 and 2 consist of three Mn(2+) (d(5)) and one Mn(3+) (d(4)) per formula unit and that of 3 has three Fe(2+) (d(6)) and one Fe(3+) (d(5)). Bond valence sums reveal that, in the α phase, the trivalent site adopts distorted tetrahedral M(1)(3+)O(4) coordination and, in the β phase, distorted trigonal-bipyramidal M(4)(3+)O(5). Thus far, the iron phase has only been isolated in the α form presumably because of little extra stabilization energy gain if the Fe(2+) d(6) ion were to occupy the M(1)O(4) site. The possible origins pertaining to the structural differences in the α and β forms are discussed.