Photo-induced optical activity in phase-change memory materials.

We demonstrate that optical activity in amorphous isotropic thin films of pure Ge2Sb2Te5 and N-doped Ge2Sb2Te5N phase-change memory materials can be induced using rapid photo crystallisation with circularly polarised laser light. The new anisotropic phase transition has been confirmed by circular dichroism measurements. This opens up the possibility of controlled induction of optical activity at the nanosecond time scale for exploitation in a new generation of high-density optical memory, fast chiroptical switches and chiral metamaterials.

Control of Ag nanoparticle distribution influencing bioactive and antibacterial properties of Ag-doped mesoporous bioactive glass particles prepared by spray pyrolysis.

Mesoporous bioactive glasses (MBGs) have become important bone implant materials because of their high specific surface area resulting in high bioactivity. Doping MBGs with Ag removes one of the remaining challenges to their applications, namely their lack of intrinsic antibacterial properties. In present work we demonstrate that Ag-doped MBGs can be prepared in one-step spray pyrolysis (SP) process. The SP preparation method offers the advantages of short processing times and continuous production over the sol-gel method previously used to prepare MBGs. Using scanning electron microscopy, transmission electron microscopy, and selected area electron diffraction we demonstrate that the synthesized MBG particles have amorphous structure with nanocrystalline Ag inclusions. The scanning transmission electron microscopy-X-ray energy dispersive spectrometry of cross-sectional samples shows that the distribution of the Ag dopant nanoparticles within MBGs can be controlled by using the appropriate formulation of the precursors. The distribution of the Ag dopant nanoparticles within the MBG particles was found to affect their surface areas, bioactivities and antibacterial properties. Based on the observations, we propose a mechanism describing MBG particle formation and controlling dopant distribution.

Impurity induced non-bulk stacking in chemically exfoliated h-BN nanosheets.

Structural characterization of 2D nanomaterials is an important step towards their future applications. In this work we carried out imaging and structural analysis of 2D h-BN produced by chemical-exfoliation, emphasizing the stacking order in few-layer sheets. Our analysis, for the first time has shown conclusively that non-bulk stacking can exist in 2D h-BN.

Controlled radiation damage and edge structures in boron nitride membranes.

We show that hexagonal boron nitride membranes synthesized by chemical exfoliation are more resistant to electron beam irradiation at 80 kV than is graphene, consistent with quantum chemical calculations describing the radiation damage processes. Monolayer hexagonal boron nitride does not form vacancy defects or amorphize during extended electron beam irradiation. Zigzag edge structures are predominant in thin membranes for both a freestanding boron nitride monolayer and for a supported multilayer step edge. We have also determined that the elemental termination species in the zigzag edges is predominantly N.

Contact angles of diiodomethane on silicon-doped diamond-like carbon coatings in electrolyte solutions.

The influence of surrounding electrolyte type and concentration on the contact angle of hydrophobic diiodomethane on silicon-doped diamond-like carbon (DLC) coatings was examined to provide insight into how the presence of electrolytes in the solution influences adhesion of hydrophobic material to doped DLC surfaces. There was a small but statistically significant increase of contact angle with increasing electrolyte concentration over the range from 0 to approximately 0.01 M, after which the contact angle was virtually unaffected by further increase in the concentration of electrolyte. It was shown that CaCl(2) has a stronger influence on the change of the contact angle than NaCl, and that an increase in Si content in the DLC coatings increased the change in the contact angle of diiodomethane for all types of electrolyte. These observations suggest that the adhesion to the Si-doped DLC surfaces is reduced by addition of the electrolytes to the surrounding solvent. This could be explained by increased ion adsorption on the DLC surface with increase in silicon doping, causing the surfaces to be more hydrophilic.

Adhesion of protein residues to substituted (111) diamond surfaces: an insight from density functional theory and classical molecular dynamics simulations.

Protein-repellent diamond coatings have great potential value for surface coatings on implants and surgical instruments. The design of these coatings relies on a fundamental understanding of the intermolecular interactions involved in the adhesion of proteins to surfaces. To get insight into these interactions, adhesion energies of glycine to pure and Si and N-doped (111) diamond surfaces represented as clusters were calculated in the gas phase, using density functional theory (DFT) at the B3LYP/6-31G* level. The computed adhesion energies indicated that adhesion of glycine to diamond surface may be modified by introducing additional elements into the surface. The adhesion was also found to induce considerable change in the conformation of glycine when compared with the lowest-energy conformer of the free molecule. In the Si and N-substituted diamond clusters, notable changes in the structures involving the substituents atoms when compared with smaller parent molecules, such as 1-methyl-1-silaadamantane and 1-azaadamantane, were detected. Adhesion free energy differences were estimated for a series of representative peptides (hydrophobic Phe-Gly-Phe, amphiphilic Arg-Gly-Phe, and hydrophilic Arg-Gly-Arg) to a (111) diamond surface substituted with different amounts of N, Si, or F, using molecular dynamics simulations in an explicit water environment employing a Dreiding force field. The calculations were in agreement with the DFT results in that adsorption of the studied peptides to diamond surface is influenced by introducing additional elements to the surface. It has been shown that, in general, substitution will enhance electrostatic interactions between a surface and surrounding water, leading to a weaker adhesion of the studied peptides.

Molecular structures of arachno-decaborane derivatives 6,9-X2B8H10 (X = CH2, NH, Se) including a gas-phase electron-diffraction study of 6,9-C2B8H14.

The molecular structures of the three heterodecaboranes arachno-6,9-C2B8H14, arachno-6,9-N2B8H12, and arachno-6,9-Se2B8H10 have been determined by ab initio MO theory. In addition, the structure of arachno-6,9-C2B8H14 was experimentally determined using gas-phase electron diffraction (GED). The accuracy of all four of these structures has been confirmed by the good agreement of the (11)B chemical shifts calculated at the GIAO-MP2 level with the experimental values. A comparison of the GIAO-HF and GIAO-MP2 methods shows that for these heteroborane clusters, electron correlation effects on the computed delta((11)B) values are quite substantial and that it is necessary to go beyond the HF level in the NMR computation.

Molecular structures of Se(SCH3)2 and Te(SCH3)2 using gas-phase electron diffraction and ab initio and DFT geometry optimisations.

The molecular structures of Se(SCH(3))(2) and Te(SCH(3))(2) were investigated using gas-phase electron diffraction (GED) and ab initio and DFT geometry optimisations. While parameters involving H atoms were refined using flexible restraints according to the SARACEN method, parameters that depended only on heavy atoms could be refined without restraints. The GED-determined geometric parameters (r(h1)) are: rSe-S 219.1(1), rS-C 183.2(1), rC-H 109.6(4) pm; angleS-Se-S 102.9(3), angleSe-S-C 100.6(2), angleS-C-H (mean) 107.4(5), phiS-Se-S-C 87.9(20), phiSe-S-C-H 178.8(19) degrees for Se(SCH(3))(2), and rTe-S 238.1(2), rS-C 184.1(3), rC-H 110.0(6) pm; angleS-Te-S 98.9(6), angleTe-S-C 99.7(4), angleS-C-H (mean) 109.2(9), phiS-Te-S-C 73.0(48), phiTe-S-C-H 180.1(19) degrees for Te(SCH(3))(2). Ab initio and DFT calculations were performed at the HF, MP2 and B3LYP levels, employing either full-electron basis sets [3-21G(d) or 6-31G(d)] or an effective core potential with a valence basis set [LanL2DZ(d)]. The best fit to the GED structures was achieved at the MP2 level. Differences between GED and MP2 results for rS-C and angleS-Te-S were explained by the thermal population of excited vibrational states under the experimental conditions. All theoretical models agreed that each compound exists as two stable conformers, one in which the methyl groups are on the same side (g(+)g(-) conformer) and one in which they are on different sides (g(+)g(+) conformer) of the S-Y-S plane (Y = Se, Te). The conformational composition under the experimental conditions could not be resolved from the GED data. Despite GED R-factors and ab initio and DFT energies favouring the g(+)g(+) conformer, it is likely that both conformers are present, for Se(SCH(3))(2) as well as for Te(SCH(3))(2).

Three-membered ring or open chain molecule - (F3C)F2SiONMe2 a model for the alpha-effect in silicon chemistry.

(F3C)F2SiONMe2 was prepared from LiONMe2 and F3CSiF3. It was characterized by gas IR and multinuclear solution NMR spectroscopy and by mass spectrometry. Its structure was elucidated by single crystal X-ray crystallography and by gas electron diffraction. (It exists as a conformer mixture.) Important findings were extremely acute SiON angles [solid 74.1(1) degrees , gas anti 84.4(32) degrees and gauche 87.8(20) degrees] and short Si...N distances [solid 1.904(2) A]. The bending potential of the SiON unit was calculated at the MP2/6-311++G(3df,2dp) level of theory and appears very flat and highly asymmetric. The calculated atomic charges (NPA) are counterintuitive to the expected behavior for a classical Si-N dative bond, as upon formation of the Si...N bond electron density is transferred mainly from oxygen to nitrogen, while the silicon charge is almost unaffected. Despite the molecular topology of a three-membered ring, the topology of the electron density shows neither a bond critical point between Si and N atoms nor a ring critical point, but the electron density and Laplacian values are related to other hypercoordinate Si compounds. The electronic properties of (F3C)F2SiONMe2 were compared to those of the adduct (F3C)F2(MeO)Si-NMe3, whose properties and structure were also calculated. The charge distribution and Laplacian values along the Si-N vectors in both molecules are similar but not equivalent. (F3C)F2SiONMe2 contains thus a nonclassical Si...N bond, and its properties can be regarded as a new model for the explanation of the old postulate of an alpha-effect in silicon chemistry, explaining the behavior of compounds with geminal Si and N atoms.

(Dimethylaminomethyl)trifluorosilane, Me2NCH2SiF3--a model for the alpha-effect in aminomethylsilanes.

F3SiCH2NMe2 was prepared as a model for the investigation of the nature of the alpha-effect in alpha-aminosilanes, by fluorination of Cl3SiCH2NMe2 with SbF3. Under less mild conditions Si--C bond cleavage was also observed, leading to the double adduct F4Si(Me2NCH2SiF3)2, which was characterised by a crystal structure analysis showing that the central SiF4 unit is connected to Me2NCH2SiF3 via SiN dative bonds and FSi contacts. F3SiCH2NMe2 was characterised by multinuclear NMR spectroscopy (1H, 13C, 15N, 19F and 29Si), gas-phase IR spectroscopy and mass spectrometry. It is a dimer in the crystal (X-ray diffraction, crystal grown in situ), held together by two Si--N dative bonds. In solution and in the gas phase the compound is monomeric. The structure of the free molecule, determined by gas-phase electron diffraction, showed that, in contrast to former postulates, there are no attractive SiN interactions. Ab initio calculations have been carried out to explain the nature of the bonding. F3SiCH2NMe2 has an extremely flat bending potential for the Si-C-N angle; the high degree of charge transfer from the Si to the N atoms which occurs upon closing the Si-C-N angle is in the opposite direction to that expected for a dative bond. The topology of the electron density of F3SiCH2NMe2 was analysed. Solvent simulation calculations have shown virtually no structural dependence on the medium surrounding the molecule. The earlier postulate of Si-->N dative bonds in SiCN systems is discussed critically in light of the new results.

Unusual structural and energetic features of homolytic bond dissociation: from tetrakis(disyl)diphosphine to tetrakis(di-tert-butylsilyl)hydrazine.

Quantum chemical calculations of the structures and thermodynamics of homolytic dissociation of the central P-P and N-N bonds in tetrakis(disyl)diphosphine and tetrakis(di-tert-butylsilyl)hydrazine have been performed. The theory predicted negative standard enthalpies for homolytic bond dissociation in both cases, -71.0 and -108.4 kJ mol(-1) for the diphosphine and hydrazine, respectively, using the ONIOM (MP2/6-31+G*:B3LYP/3-21G*) level. The dissociation is accompanied by considerable structural changes in the radicals as compared to the corresponding fragments of the parent molecules, resulting in low dissociation enthalpies. The most pronounced changes in both radicals are the relaxation of bond angles in the substituents and a conformational change in the orientation of the substituent groups. In addition, the bis(di-tert-butylsilyl)aminyl radical displays a considerable increase in Si-N-Si angle and shortening of the Si-N bonds upon dissociation. These changes are not associated with any appreciable delocalisation of the lone electron, as the spin density is found from the B3LYP/3-21G* calculations to be largely concentrated on the nitrogen atom. It has been also shown that although the dissociation energies are low for both compounds, the intrinsic energies of the central bonds are still high, 140.6 kJ mol(-1) for the P-P bond in tetrakis(disyl)diphosphine and 490.6 kJ mol(-1) for the N-N bond in tetrakis(di-tert-butylsilyl)hydrazine, using the ONIOM method. The calculations predict that the dissociation of tetrakis(disyl)diphosphine would have negative free energy even without taking relaxation of the fragments into account, while the full potential of releasing about 306 kJ mol(-1) of energy stored in the ligands of tetrakis(di-tert-butylsilyl)hydrazine is only fully realised upon a considerable separation of the fragments.

The molecular structure of [Sn(P2C2But2)] using gas-phase electron diffraction and DFT calculations.

The molecular structure of 2,4-di-tert-butyl-eta4-1,3-diphosphacyclobutadiene tin has been determined in the gas phase by electron diffraction using both the DYNAMITE and SARACEN methods. The suitability of many different theoretical methods for the calculation of structures of half-sandwich main-group metal complexes has been investigated, and, by comparison of the results with the experimental structures, suggestions have been made as to the most suitable methods for this class of compound.

Gas-phase electron diffraction studies of the icosahedral carbaboranes, ortho-, meta- and para-C2B10H12.

The molecular structures of the three closo-carbaboranes, ortho-, meta- and para-C2B10H12, were experimentally determined using gas-phase electron diffraction (GED). All unique bond distances for ortho and meta carbaboranes were determined experimentally for the first time. For ortho-carbaborane (RG= 0.046), a model with C2v symmetry refined to give bond distances of 1.624(8) A for C-C, 1.093(8)A for C-H and 1.192(3)-1.196(3) A for B-H. For meta-carbaborane (RG= 0.040) a model with C2v symmetry refined to give a CC distance of 2.575(9) A. For para-carbaborane (RG= 0.062) a model with D5d symmetry refined to give a C-B bond distance of 1.698(3) A, B2-B3 of 1.785(1), B2-B7 of 1.774(4) and CC of 3.029(5)A. These GED structures are compared with geometries from other experimental diffraction methods (neutron, X-ray) and ab initio calculations.

An enormous vibrational motion: the gas-phase structure of dimethyl-bis(methoxyethynyl) germanium.

The structure of dimethyl-bis(methoxyethynyl) germanium has been determined in the gas phase by electron diffraction utilising flexible restraints from quantum chemical calculations. Theoretical methods (B3LYP/6-311+G* and MP2/6-311+G*) predict a low barrier to rotation of the methoxy groups in the molecule in addition to low-frequency vibrations of the long ethynyl chains. In the equilibrium structure the Ge-C[triple bond]C angles of the two methoxyethynyl fragments in the molecule are computed to deviate by up to 4 degrees from the linear arrangement. As a consequence of low-frequency large-amplitude vibrational motion the experimental structure of these fragments without applying vibrational corrections deviates considerably from linearity, while the structure corrected for vibrational effects using the harmonic approximation and taking into account a non-linear transformation between internal and Cartesian coordinates (r(h1)) shows closer agreement with theory. The main experimental structural parameters of dimethyl-bis(methoxyethynyl) germanium (r(h1)) are: r(Ge-C)(mean), 192.5(1) pm; DeltaGeC =r(Ge-C(methyl))-r(Ge-C(ethynyl)), 4.5(5) pm, r(C[triple bond]C)(mean), 122.8(2) pm; r(C-O)(mean), 138.9(3) pm; DeltaCO =r(C(methyl)-O)-r(C(ethynyl)-O), 14.5(2) pm, r(C-H)(mean), 109.1(4) pm; [angle](X-C-H)(mean)(X = Ge,O), 109(1) degree; [angle]C(ethynyl)-Ge-C(ethynyl), 108.1(4) degree; [angle]C(methyl)-Ge-C(methyl), 113.4(5) degree; [angle]Ge-C[triple bond]C, 163(1) degree; [angle]C[triple bond]C-O, 176(2) degree; [angle]C-O-C, 115.2(6) degree; methoxy group torsion, tau, 36(9) degree from the position in which the C-O bond eclipses the further Ge-C(ethynyl) bond.

The molecular structure of tetra-tert-butyldiphosphine: an extremely distorted, sterically crowded molecule.

The molecular structure of tetra-tert-butyldiphosphine has been determined in the gas phase by electron diffraction using the new DYNAMITE method and in the crystalline phase by X-ray diffraction. Ab initio methods were employed to gain a greater understanding of the structural preferences of this molecule in the gas phase, and to determine the intrinsic P-P bond energy, using recently described methods. Although the P-P bond is relatively long [GED 226.4(8) pm; X-ray 223.4(1) pm] and the dissociation energy is computed to be correspondingly small (150.6 kJ mol(-1)), the intrinsic energy of this bond (258.2 kJ mol(-1)) is normal for a diphosphine. The gaseous data were refined using the new Edinburgh structure refinement program ed@ed, which is described in detail. The molecular structure of gaseous P(2)Bu(t)(4) is compared to that of the isoelectronic 1,1,2,2-tetra-tert-butyldisilane. The molecules adopt a conformation with C(2) symmetry. The P-P-C angles returned from the gas electron diffraction refinement are 118.8(6) and 98.9(6) degrees, a difference of 20 degrees, whilst the C-P-C angle is 110.3(8) degrees. The corresponding parameters in the crystal are 120.9(1), 99.5(1) and 109.5(1) degrees. There are also large deformations within the tert-butyl groups, making the DYNAMITE analysis for this molecule extremely important.

Molecular structure of Hf(BH4)4 investigated by quantum mechanical calculations and gas-phase electron diffraction.

The structure of the gaseous hafnium tetrakis(tetrahydroborate) molecule, Hf(BH4)4, has been investigated by detailed quantum mechanical calculations and by analysis of its gas electron-diffraction (GED) pattern. The ground-state geometry possesses T symmetry with all of the triply-bridged BH4 groups twisted equally about the Hf...B-H axes. Salient structural parameters (ra distances, r angles) deduced from the GED pattern by the SARACEN method were: r(Hf...B) 231.4(2), r(Hf-Hb) 221.5(7), r(B-Hb) 127.6(5), r(B-Ht) 121(1) pm, Hf...B-Hb 69.4(3), Hb-B-Hb 108.4(4), Hb-B-Ht 110.6(3), B...Hf...B-Hb 166(1) degrees. A notable feature is the large magnitude of the Hf...B and Hf-Hb anharmonicity parameters, attributed to the fluxional hydrogen atom exchange process. The properties are compared with those of related tetrahydroborates..

Structures of the radical P[N(SiMe3)2](NPri2), its dimer, cation and chloro derivative.

Treatment of PCl[N(SiMe3)2](NPri2) (1) with potassium-graphite in thf afforded the colourless, crystalline diphosphine [P[N(SiMe3)2](NPri2)]2 (2) in good yield. Sublimation of 2 in vacuo yielded the yellow phosphinyl radical P[N(SiMe3)2](NPri2) (3), which upon cooling reverted to 2; the latter in C6D6 at 298 K was a mixture of rac and meso diastereoisomers. The yellow, crystalline phosphenium salt [P[N(SiMe3)2](NPri2)][AlCl4] (4) was obtained from 1 and 1/2Al2Cl6 in CH2Cl2. By single-crystal X-ray diffraction (XRD) the structures of the known compound 1 and of 2 and 4 were determined. The structure of the radical 3, formed by the thermal homolytic dissociation of the diphosphine 2, was determined in the gas phase by electron diffraction (GED), utilising data from UMP2/6-31+G*ab initio calculations. The model of the molecule in the GED structure analysis was described by a set of internal coordinates and an initial set of Cartesian coordinates from ab initio calculations, facilitating the structure analysis. The experimental data were found to be consistent with the presence of a single conformer of the radical in the gas phase. The computed standard homolytic dissociation enthalpy of the P-P bond in the corresponding diphosphine 2, corrected for BSSE, 54 kJ mol(-1), is substantially reduced compared to the dissociation enthalpy of tetramethyldiphosphine by the reorganisation energies of the fragments that form upon dissociation. The intrinsic energy content of the P-P bond in the diphosphine 2 was estimated to be 286 kJ mol(-1), in agreement with the results of previous work on a series of crowded diphosphines.

Structural changes, P-P bond energies, and homolytic dissociation enthalpies of substituted diphosphines from quantum mechanical calculations.

The molecular structures of the diphosphines P(2)[CH(SiH(3))(2)](4), P(2)[C(SiH(3))(3)](4), P(2)[SiH(CH(3))(2)](4), and P(2)[Si(CH(3))(3)](4) and the corresponding radicals P[CH(SiH(3))(2)](2), P[C(SiH(3))(3)](2), P[SiH(CH(3))(2)](2), and P[Si(CH(3))(3)](2) were predicted by theoretical quantum chemical calculations at the HF/3-21G*, B3LYP/3-21G*, and MP2/6-31+G* levels. The conformational analyses of all structures found the gauche conformers of the diphosphines with C(2) symmetry to be the most stable. The most stable conformers of the phosphido radicals were also found to possess C(2) symmetry. The structural changes upon dissociation allow the release of some of the energy stored in the substituents and therefore contribute to the decrease of the P-P bond dissociation energy. The P-P bond dissociation enthalpies at 298 K in the compounds studied were calculated to vary from -11.4 kJ mol(-1) (P(2)[C(SiH(3))(3)](4)) to 179.0 kJ mol(-1) (P(2)[SiH(CH(3))(2)](4)) at the B3LYP/3-21G* level. The MP2/6-31+G* calculations predict them to be in the range of 52.8-207.9 kJ mol(-1). All the values are corrected for basis set superposition error. The P-P bond energy defined by applying a mechanical analogy of the flexible substituents connected by a spring shows less variation, between 191.3 and 222.6 kJ mol(-1) at the B3LYP/3-21G level and between 225.6 and 290.4 kJ mol(-1) at the MP2/6-31+G* level. Its average value can be used to estimate bond dissociation energies from the energetics of structural relaxation.