First-principle study of adsorption of hydrogen on ti-doped Mg(0001) surface

Ab initio density functional theory (DFT) calculations are performed to study the adsorption of H2 molecules on a Ti-doped Mg(0001) surface. We find that two hydrogen molecules are able to dissociate on top of the Ti atom with very small activation barriers (0.103 and 0.145 eV for the first and second H2 molecules, respectively). Additionally, a molecular adsorption state of H2 above the Ti atom is observed for the first time and is attributed to the polarization of the H2 molecule by the Ti cation. Our results parallel recent findings for H2 adsorption on Ti-doped carbon nanotubes or fullerenes. They provide new insight into the preliminary stages of hydrogen adsorption onto Ti-incorporated Mg surfaces.

Ab initio studies of hydrogen desorption from low index magnesium hydride surface

The low index Magnesium hydride surfaces, MgH2(0 0 1) and MgH2(1 1 0), have been studied by ab intio Density Functional Theory (DFT) calculations. It was found that the MgH2(1 1 0) surface is more stable than MgH2(0 0 1) surface, which is in good agreement with the experimental observation. The H2 desorption barriers vary depending on the crystalline surfaces that are exposed and also the specific H atom sites involved – they are found to be generally high, due to the thermodynamic stability of the MgH2 system, and are larger for the MgH2(0 0 1) surface. The pathway for recombinative desorption of one in-plane and one bridging H atom from the MgH2(1 1 0) surface was found to be the lowest energy barrier amongst those computed (172 KJ/mol) and is in good agreement with the experimental estimates.

Atomic hydrogen diffusion in novel magnesium nanostructures : the impact of incorporated subsurface carbon atoms

Ab initio Density Functional Theory (DFT) calculations are performed to study the diffusion of atomic hydrogen on a Mg(0001) surface and their migration into the subsurface layers. A carbon atom located initially on a Mg(0001) surface can migrate into the sub-surface layer and occupy a fcc site, with charge transfer to the C atom from neighboring Mg atoms. The cluster of postively charged Mg atoms surrounding a sub-surface C is then shown to facilitate the dissociative chemisorption of molecular hydrogen on the Mg(0001) surface, and the surface migration and subsequent diffusion into the subsurface of atomic hydrogen. This helps rationalize the experimentally-observed improvement in absorption kinetics of H2 when graphite or single walled carbon nanotubes (SWCNT) are introduced into the Mg powder during ball milling.

Catalytic effects of subsurface carbon in the chemisorption of hydrogen on a Mg(0001) surface: an ab-initio study

Ab initio density functional theory (DFT) calculations are performed to explore possible catalytic effects on the dissociative chemisorption of hydrogen on a Mg(0001) surface when carbon is incorporated into Mg materials. The computational results imply that a C atom located initially on a Mg(0001) surface can migrate into the subsurface and occupy an fcc interstitial site, with charge transfer to the C atom from neighboring Mg atoms. The effect of subsurface C on the dissociation of H2 on the Mg(0001) surface is found to be relatively marginal: a perfect sublayer of interstitial C is calculated to lower the barrier by 0.16 eV compared with that on a pure Mg(0001) surface. Further calculations reveal, however, that sublayer C may have a significant effect in enhancing the diffusion of atomic hydrogen into the sublayers through fcc channels. This contributes new physical understanding toward rationalizing the experimentally observed improvement in absorption kinetics of H2 when graphite or single walled carbon nanotubes (SWCNT) are introduced into the Mg powder during ball milling.

Calibration of the electron volt spectrometer, a deep inelastic neutron scattering spectrometer at the ISIS pulsed neutron spallation source

The electron Volt Spectrometer (eVS) is an inverse geometry filter difference spectrometer that has been optimised to measure the single atom properties of condensed matter systems using a technique known as Neutron Compton Scattering (NCS) or Deep Inelastic Neutron Scattering (DINS). The spectrometer utilises the high flux of epithermal neutrons that are produced by the ISIS neutron spallation source enabling the direct measurement of atomic momentum distributions and ground state kinetic energies. In this paper the procedure that is used to calibrate the spectrometer is described. This includes details of the method used to determine detector positions and neutron flight path lengths as well as the determination of the instrument resolution. Examples of measurements on 3 different samples are shown, ZrH2, 4He and Sn which show the self-consistency of the calibration procedure.

Molecular cocrystals of 5-(4-bromophenyl)-1,3,4-thiadiazol-2-amine: hydrogen bonding in the structures of the 1:1 adduct with 2-(naphthalen-2-yloxy)acetic acid and the salt with 3,5-dinitrobenzoic acid

The structures of the anhydrous products from the interaction of 2-amino-5-(4-bromophenyl)-1,3,4-thiadiazole with (2-naphthoxy)acetic acid, the 1:1 adduct C8H6BrN3S . C12H10O3 (I) and 3,5-dinitrobenzoic acid, the salt C8H7BrN3S+ C7H3N2O6- (II) have been determined. In the adduct (I), a heterodimer is formed through a cyclic hydrogen-bonding motif [graph set R2/2(8)], involving carboxylic acid O-H...N(hetero)and amine N-H...O(carboxyl) interactions. The heterodimers are essentially planar with a thiadiazole to naphthyl ring dihedral angle of 15.9(2)deg. and the intramolecular thiadiazole to phenyl ring angle of 4.7(2)deg. An amine N-H...N(hetero) hydrogen bond between the heterodimers generates a one-dimensional chain structure extending down [001]. Also present are weak benzene-benzene and naphthalene-naphthalene pi-pi stacking interactions down the b axis [minimum ring centroid separation, 3.936(3) Ang.]. With the salt (II), the cation-anion association is also through a cyclic R2/2(8) motif but involving duplex N-H...O(carboxyl) hydrogen bonds, giving a heterodimer which is close to planar [dihedral angles between the thiadiazole ring and the two benzene rings, 5.00(16)deg. (intra) and 7.23(15)deg. (inter)]. A secondary centrosymmetric cyclic N-H...O(carboxyl) hydrogen-bonding association involving the second amino H-atom generates a heterotetramer. Also present in the crystal are weak pi-pi i-\p interactions between thiadiazolium rings [minimum ring centroid separation, 3.936(3)Ang.], as well as a short Br...O(nitro) interaction [3.314(4)Ang.]. The two structures reported here now provide a total of three crystallographically characterized examples of co-crystalline products from the interaction of 2-amino-5-(4-bromophenyl)-1,3,4-thiadiazole with carboxylic acids, of which only one involves proton-transfer.

Breaking time-inversion invariance through decoherence : energetic consequences for attosecond neutron scattering

Nuclei and electrons in condensed matter and/or molecules are usually entangled, due to the prevailing (mainly electromagnetic) interactions. However, the "environment" of a microscopic scattering system (e.g. a proton) causes ultrafast decoherence, thus making atomic and/or nuclear entanglement e®ects not directly accessible to experiments. However, our neutron Compton scattering experiments from protons (H-atoms) in condensed systems and molecules have a characteristic collisional time about 100|1000 attoseconds. The quantum dynamics of an atom in this ultrashort, but ¯nite, time window is governed by non-unitary time evolution due to the aforementioned decoherence. Unexpectedly, recent theoretical investigations have shown that decoherence can also have the following energetic consequences. Disentangling two subsystems A and B of a quantum system AB is tantamount to erasure of quantum phase relations between A and B. This erasure is widely believed to be an innocuous process, which e.g. does not a®ect the energies of A and B. However, two independent groups proved recently that disentangling two systems, within a su±ciently short time interval, causes increase of their energies. This is also derivable by the simplest Lindblad-type master equation of one particle being subject to pure decoherence. Our neutron-proton scattering experiments with H2 molecules provide for the first time experimental evidence of this e®ect. Our results reveal that the neutron-proton collision, leading to the cleavage of the H-H bond in the attosecond timescale, is accompanied by larger energy transfer (by about 2|3%) than conventional theory predicts. Preliminary results from current investigations show qualitatively the same e®ect in the neutron-deuteron Compton scattering from D2 molecules. We interpret the experimental findings by treating the neutron-proton (or neutron-deuteron) collisional system as an entangled open quantum system being subject to fast decoherence caused by its "environment" (i.e., two electrons plus second nucleus of H2 or D2). The presented results seem to be of generic nature, and may have considerable consequences for various processes in condensed matter and molecules, e.g. in elementary chemical reactions.

Nanostructured metal hydrides for hydrogen storage studied by in situ synchrotron and neutron diffraction

This work was focused on studies of the metal hydride materials having a potential in building hydrogen storage systems with high gravimetric and volumetric efficiencies of H storage and formed / decomposed with high rates of hydrogen exchange. In situ diffraction studies of the metal-hydrogen systems were explored as a valuable tool in probing both the mechanism of the phase-structural transformations and their kinetics. Two complementary techniques, namely Neutron Powder Diffraction (NPD) and Synchrotron X-ray diffraction (SR XRD) were utilised. High pressure in situ NPD studies were performed at D2 pressures reaching 1000 bar at the D1B diffractometer accommodated at Institute Laue Langevin, Grenoble. The data of the time resolved in situ SR XRD were collected at the Swiss Norwegian Beam Lines, ESRF, Grenoble in the pressure range up to 50 bar H2 at temperatures 20-400°C. The systems studied by NPD at high pressures included deuterated Al-modified Laves-type C15 ZrFe2-xAlx intermetallics with x = 0.02; 0.04 and 0.20 and the CeNi5-D2 system. D content, hysteresis of H uptake and release, unit cell expansion and stability of the hydrides systematically change with Al content. Deuteration exhibited a very fast kinetics; it resulted in increase of the unit cells volumes reaching 23.5 % for ZrFe1.98Al0.02D2.9(1) and associated with exclusive occupancy of the Zr2(Fe,Al)2 tetrahedra. For CeNi5 deuteration yielded a hexahydride CeNi5D6.2 (20°C, 776 bar D2) and was accompanied by a nearly isotropic volume expansion reaching 30.1% (∆a/a=10.0%; ∆c/c=7.5%). Deuterium atoms fill three different interstitial sites including Ce2Ni2, Ce2Ni3 and Ni4. Significant hysteresis was observed on the first absorption-desorption cycle. This hysteresis decreased on the absorption-desorption cycling. A different approach to the development of H storage systems is based on the hydrides of light elements, first of all the Mg-based ones. These systems were studied by SR XRD. Reactive ball milling in hydrogen (HRBM) allowed synthesis of the nanostructured Mg-based hydrides. The experimental parameters (PH2, T, energy of milling, ball / sample ratio and balls size), significantly influence rate of hydrogenation. The studies confirmed (a) a completeness of hydrogenation of Mg into MgH2; (b) indicated a partial transformation of the originally formed -MgH2 into a metastable -MgH2 (a ratio / was 3/1); (c) yielded the crystallite size for the main hydrogenation product, -MgH2, as close to 10 nm. Influence of the additives to Mg on the structure and hydrogen absorption/desorption properties and cycle behaviour of the composites was established and will be discussed in the paper.

Location of hydrogen atoms in hydronium jarosite

Various models for the crystal structure of hydronium jarosite were determined from Rietveld refinements against neutron powder diffraction patterns collected at ambient temperature and also single-crystal X-ray diffraction data. The possibility of a lower symmetry space group for hydronium jarosite that has been suggested by the literature was investigated. It was found the space group is best described as R3¯m, the same for other jarosite minerals. The hydronium oxygen atom was found to occupy the 3¯m site (3a Wyckoff site). Inadequately refined hydronium bond angles and bond distances without the use of restraints are due to thermal motion and disorder of the hydronium hydrogen atoms across numerous orientations. However, the acquired data do not permit a precise determination of these orientations; the main feature up/down disorder of hydronium is clear. Thus, the highest symmetry model with the least disorder necessary to explain all data was chosen: The hydronium hydrogen atoms were modeled to occupy an m (18 h Wyckoff site) with 50 % fractional occupancy, leading to disorder across two orientations. A rigid body description of the hydronium ion rotated by 60° with H–O–H bond angles of 112° and O–H distances of 0.96 Å was optimal. This rigid body refinement suggests that hydrogen bonds between hydronium hydrogen atoms and basal sulfate oxygen atoms are not predominant. Instead, hydrogen bonds are formed between hydronium hydrogen atoms and hydroxyl oxygen atoms. The structure of hydronium alunite is expected to be similar given that alunite supergroup minerals are isostructural.

Poly[mu5-{hydrogen bis[(E)-cinnamato]}-caesium

In the structure of the title polymeric complex [Cs2(C9H7O2)(C9H8O2)]n, the Cs salt-adduct of trans-cinnamic acid, the Cs+ ions of the two individual irregular CsO8 coordination polyhedra lie on a twofold rotation axis and are linked by four bridging carboxyl O-donors from the two cinnamate ligand species. These two ligand components are inter-linked through a delocalized H atom within a short O...H...O hydrogen bond. Structure extension gives a two-dimensional coordination polymer which lies parallel to (001). The crystal was determined from a crystal twinned by non-merohedry, with a twin component ratio of approximately 1:1.

Three-dimensional hydrogen-bonded structures in the hydrated proton-transfer salts of isonipecotamide with the dicarboxylic oxalic and adipic acid analogues

The structures of the 1:1 hydrated proton-transfer compounds of isonipecotamide (piperidine-4-carboxamide) with oxalic acid, 4-carbamoylpiperidinium hydrogen oxalate dihydrate, C6H13N2O+·C2HO4-·2H2O, (I), and with adipic acid, bis­(4-car­bam­oylpiperidinium) adipate dihydrate, 2C6H13N2O+·C6H8O42-·2H2O, (II), are three-dimensional hydrogen-bonded constructs involving several different types of enlarged water-bridged cyclic associations. In the structure of (I), the oxalate monoanions give head-to-tail carb­oxy­lic acid O-HOcarboxyl hydrogen-bonding inter­actions, forming C(5) chain substructures which extend along a. The isonipecotamide cations also give parallel chain substructures through amide N-HO hydrogen bonds, the chains being linked across b and down c by alternating water bridges involving both carboxyl and amide O-atom acceptors and amide and piperidinium N-HOcarboxyl hydrogen bonds, generating cyclic R43(10) and R32(11) motifs. In the structure of (II), the asymmetric unit comprises a piperidinium cation, half an adipate dianion, which lies across a crystallographic inversion centre, and a solvent water mol­ecule. In the crystal structure, the two inversion-related cations are inter­linked through the two water mol­ecules, which act as acceptors in dual amide N-HOwater hydrogen bonds, to give a cyclic R42(8) association which is conjoined with an R44(12) motif. Further N-HOwater, water O-HOamide and piperidinium N-HOcarbox­yl hydrogen bonds give the overall three-dimensional structure. The structures reported here further demonstrate the utility of the isonipecotamide cation as a synthon for the generation of stable hydrogen-bonded structures. The presence of solvent water mol­ecules in these structures is largely responsible for the non-occurrence of the common hydrogen-bonded amide-amide dimer, promoting instead various expanded cyclic hydrogen-bonding motifs.

Hydrogen-bonded two- and three-dimensional polymeric structures in the ammonium salts of 3,5-dinitrobenzoic acid, 4-nitrobenzoic acid and 2,4-dichlorobenzoic acid

The structures of the ammonium salts of 3,5-dinitrobenzoic acid, NH4+ C7H3N2O6- (I), 4-nitrobenzoic acid, NH4+ C7H4N2O4- . 2H2O (II) and 2,4-dichlorobenzoic acid, NH4+ C7H3Cl2O2- . 0.5H2O (III), have been determined and their hydrogen-bonded structures are described. All salts form hydrogen-bonded polymeric structures, three-dimensional in (I) and two-dimensional in (II) and (III). With (I), a primary cation-anion cyclic association is formed [graph set R3/4(10)] through N-H...O hydrogen bonds, involving a carboxyl O,O' group on one side and a single carboxyl O-atom on the other. Structure extension involves both N-H...O hydrogen bonds to both carboxyl and nitro O-atom acceptors. With structure (II), the primary inter-species interactions and structure extension into layers lying parallel to (0 0 1) are through conjoined cyclic hydrogen-bonding motifs: R3/4(10) [one cation, a carboxyl (O,O') group and two water molecules] and centrosymmetric R2/4(8) [two cations and two water molecules]. The structure of (III) also has conjoined R3/4(10) and centrosymmetric R2/4(8) motifs in the layered structure but these differ in that he first involves one cation, a carboxyl (O,O') as well as a carboxyl (O) group and one water molecule, the second, two cations and two carboxyl O-groups. The layers lie parallel to (1 0 0). The structures of the salt hydrates (II) and (III) reported in this work, giving two-dimensional layered arrays through conjoined hydrogen-bonded nets provide further illustrations of a previously indicated trend among ammonium salts of carboxylic acids, but the anhydrous three-dimensional structure of (I) is inconsistent.

Crystal structures and hydrogen bonding in the anhydrous tryptaminium salts of the isomeric (2,4-dichlorophenoxy)acetic and (3,5-dichlorophenoxy)acetic acids

The anhydrous salts of 1H-indole-3-ethanamine (tryptamine) with isomeric (2,4-dichlorophenoxy)acetic acid (2,4-D) and (3,5-dichlorophenoxy)acetic (3,5-D), C10H13N2+ (C8H5Cl2O3)-, [(I) and (II), respectively] have been determined and their one-dimensional hydrogen-bonded polymeric structures are described. In the crystal of (I),the aminium H-atoms are involved in three separate inter-species N-H...O hydrogen-bonding interactions, two with carboxyl O-atom acceptors and the third in an asymmetric three-centre bidentate carboxyl O,O' chelate [graph set R2/1(4)]. The indole H-atom forms an N-H...O~carboxyl~ hydrogen bond, extending the chain structure along the b axial direction. In (II), two of the three aminium H-atoms are also involved in N-H...O(carboxyl) hydrogen bonds similar to (I) but with the third, a three-centre asymmetric interaction with carboxyl and phenoxy O-atoms is found [graph set R2/1(5)]. The chain polymeric extension is also along b. There are no pi--pi ring interactions in either of the structures. The aminium side chain conformations differ significantly between the two structures, reflecting the conformational ambivalence of the tryptaminium cation, as found also in the benzoate salts.

The three-dimensional hydrogen-bonded structures in the ammonium and sodium salt hydrates of 4-aminophenylarsonic acid

The structures of two hydrated salts of 4-aminophenylarsonic acid (p-arsanilic acid), namely ammonium 4-aminophenylarsonate monohydrate, NH4(+)·C6H7AsNO3(-)·H2O, (I), and the one-dimensional coordination polymer catena-poly[[(4-aminophenylarsonato-κO)diaquasodium]-μ-aqua], [Na(C6H7AsNO3)(H2O)3]n, (II), have been determined. In the structure of the ammonium salt, (I), the ammonium cations, arsonate anions and water molecules interact through inter-species N-H...O and arsonate and water O-H...O hydrogen bonds, giving the common two-dimensional layers lying parallel to (010). These layers are extended into three dimensions through bridging hydrogen-bonding interactions involving the para-amine group acting both as a donor and an acceptor. In the structure of the sodium salt, (II), the Na(+) cation is coordinated by five O-atom donors, one from a single monodentate arsonate ligand, two from monodentate water molecules and two from bridging water molecules, giving a very distorted square-pyramidal coordination environment. The water bridges generate one-dimensional chains extending along c and extensive interchain O-H...O and N-H...O hydrogen-bonding interactions link these chains, giving an overall three-dimensional structure. The two structures reported here are the first reported examples of salts of p-arsanilic acid.

Crystal structures and hydrogen bonding in the morpholinium salts of four phenoxyacetic acid analogues

The anhydrous salts morpholinium (tetrahydro-2-H-1,4-oxazine) phenxyacetate, C4H10NO+ C8H7O3- (I), (4-fluorophenoxy)acetate, C4H10NO+ C8H6FO3- (II) and isomeric morpholinium (3,5-dichlorophenoxy)acetate (3,5-D) (III) and morpholinium (2,4-dichlorophenoxy)acetate (2,4-D), C4H10NO+ C8H5Cl2O3- (IV), have been determined and their hydrogen-bonded structures are described. In the crystals of (I), (III) and (IV), one of the the aminium H atoms is involved in a three-centre asymmetric cation-anion N-H...O,O' R2/1(4) hydrogen-bonding interaction with the two carboxyl O-atom acceptors of the anion. With the structure of (II), the primary N---H...O interaction is linear. In the structures of (I), (II) and (III), the second N-H...O(carboxyl) hydrogen bond generates one-dimensional chain structures extending in all cases along [100]. With (IV), the ion pairs are linked though inversion-related N-H...O hydrogen bonds [graph set R2/4(8)], giving a cyclic heterotetrameric structure.