Transition metal clusters on graphite

The topic of this work is 3d transition metals deposited on graphite. Spin-polarised density-functional calculations are used to obtain the magnetic moments of deposited adatoms and dimers. Interatomic potentials are also deduced. These are used in molecular dynamics simulations to study cluster formation and to investigate cluster morphology.

Magnetic coupling in trinuclear partial cubane copper(II) complexes with a hydroxo bridging core and peripheral phenoxo bridges from NNO donor Schiff base ligands

Three new trinuclear copper(II) complexes, [(CuL1)(3)(mu(3)-OH)](ClO4)(2)center dot 3.75H(2)O (1), [(CuL2)(3)(mu(3)-OH)](ClO4)(2) (2) and [(CuL3)(3)(mu(3)-OH)](BF4)(2)center dot 0.5CH(3)CN (3) have been synthesized from three tridentate Schiff bases HL1, HL2, and HL3 (HL1 = 2-[(2-amino-ethylimino)-methyl]-phenol, HL2 = 2-[(2-methylamino-ethylimino)-methyl]-phenol and HL3 = 2-[1-(2-dimethylamino-ethylimino)-ethyl]-phenol). The complexes are characterized by single-crystal X-ray diffraction analyses, IR, UV-vis and EPR spectroscopy, and variable-temperature magnetic measurements. All the compounds contain a partial cubane [Cu3O4] core consisting of the trinuclear unit [(CuL)(3)(mu(3)-OH)](2+) together with perchlorate or fluoroborate anions. In each of the complexes, the three copper atoms are five-coordinated with a distorted square-pyramidal geometry except in complex 1, in which one of the Cu-II ions of the trinuclear unit is six-coordinate being in addition weakly coordinated to one of the perchlorate anions. Variable-temperature magnetic measurements and EPR spectra indicate an antiferromagnetic exchange coupling between the CuII ions of complexes 1 and 2, while this turned out to be ferromagnetic for complex 3. Experimental values have been fitted according to an isotropic exchange Hamiltonian. Calculations based on Density Functional Theory have also been performed in order to estimate the exchange coupling constants in these three complexes. Both sets of values indicate similar trends and specially calculated J values establish a magneto-structural correlation between them and the Cu-O-Cu bond angle, in that the coupling is more ferromagnetic for smaller bond angle values.

Radiative efficiencies and global warming potentials using theoretically determined absorption cross-sections for several hydrofluoroethers (HFEs) and hydrofluoropolyethers (HFPEs)

Integrated infrared cross-sections and wavenumber positions for the vibrational modes of a range of hydrofluoroethers (HFEs) and hydrofluoropolyethers (HFPEs) have been calculated. Spectra were determined using a density functional method with an empirically derived correction for the wavenumbers of band positions. Radiative efficiencies (REs) were determined using the Pinnock et al. method and were used with atmospheric lifetimes from the literature to determine global warming potentials (GWPs). For the HFEs and the majority of the molecules in the HG series HFPEs, theoretically determined absorption cross-sections and REs lie within ca. 10% of those determined using measured spectra. For the larger molecules in the HG series and the HG′ series of HFPEs, agreement is less good, with theoretical values for the integrated cross-sections being up to 35% higher than the experimental values; REs are up to 45% higher. Our method gives better results than previous theoretical approaches, because of the level of theory chosen and, for REs, because an empirical wavenumber correction derived for perfluorocarbons is effective in predicting the positions of C–F stretching frequencies at around 1250 cm−1 for the molecules considered here.

The interplay of secondary Hg⋯S, Hg⋯N and Hg⋯π bonding interactions in supramolecular structures of phenylmercury(ii) dithiocarbamates

Three new phenylmercury(II) and one mercury(II) dithiocarbamate complexes viz. PhHg S2CN(PyCH2) Bz (1), PhHg S2CN(PyCH2)CH3 (2), PhHg S2CN(Bz)CH3 (3), and [Hg (NCS2(PyCH2)Bz)(2)] (4) (Py = pyridine; Bz = benzyl) have been synthesized and characterized by elemental analyses, IR, electronic absorption, H-1 and C-13 NMR spectroscopy. The crystal structures of 1, 2 and 3 showed a linear S-Hg-C core at the centre of the molecule, in which the metal atom is bound to the sulfur atom of the dithiocarbamate ligand and a carbon atom of the aromatic ring. In contrast the crystal structure of 4 showed a linear S-Hg-S core at the Hg(II) centre of the molecule. Weak intermolecular Hg center dot center dot center dot N (Py) interactions link molecules into a linear chain in the case of 1, whereas chains of dimers are formed in 2 through intermolecular Hg center dot center dot center dot N (Py) and Hg center dot center dot center dot S interactions. 3 forms a conventional face-to-edge dimeric structure through intermolecular Hg center dot center dot center dot S secondary bonding and 4 forms a linear chain of dimers through face-to-face Hg center dot center dot center dot S secondary bonding. In order to elucidate the nature of these secondary bonding interactions and the electronic absorption spectra of the complexes, ab initio quantum chemical calculations at the MP2 level and density functional theory calculations were carried out for 1-3. Complexes 1 and 2 exhibited photoluminescent properties in the solid state as well as in the solution phase. Studies indicate that Hg center dot center dot center dot S interactions decrease and Hg center dot center dot center dot N interactions increase the chances of photoluminescence in the solid phase

On the difficulties of present theoretical models to predict the oxidation state of atomic Au adsorbed on regular sites of CeO2(111)

The electronic structure and oxidation state of atomic Au adsorbed on a perfect CeO2(111) surface have been investigated in detail by means of periodic density functional theory-based calculations, using the LDA+U and GGA+U potentials for a broad range of U values, complemented with calculations employing the HSE06 hybrid functional. In addition, the effects of the lattice parameter a0 and of the starting point for the geometry optimization have also been analyzed. From the present results we suggest that the oxidation state of single Au atoms on CeO2(111) predicted by LDA+U, GGA+U, and HSE06 density functional calculations is not conclusive and that the final picture strongly depends on the method chosen and on the construction of the surface model. In some cases we have been able to locate two well-defined states which are close in energy but with very different electronic structure and local geometries, one with Au fully oxidized and one with neutral Au. The energy difference between the two states is typically within the limits of the accuracy of the present exchange-correlation potentials, and therefore, a clear lowest-energy state cannot be identified. These results suggest the possibility of a dynamic distribution of Au0 and Au+ atomic species at the regular sites of the CeO2(111) surface.

Structure and stress of Re(11%21); chiral terraces at a racemic surface

The surface structure and morphology of the clean Re(11%21) surface has been investigated through combined low energy electron diffraction intensity analysis of data taken at multiple angles of incidence, scanning tunneling microscopy, and first-principles density functional calculations. The results show how this globally racemic surface terminates in two chirally distinct terraces, which show largescale out-of-plane atomic relaxations and in-plane lateral movement of the uppermost atoms. We further identify and discuss the initial stages of step bunching upon adsorption of oxygen that leads ultimately to the large-scale faceting of the surface. Finally, we present calculations of surface stress and the response to applied surface strain, which suggest routes to the exertion of control over the expression of chirality at the surface.

Lithium and oxygen adsorption at the b-MnO2 (110) surface

The adsorption and co-adsorption of lithium and oxygen at the surface of rutile-like manganese dioxide(b-MnO2), which are important in the context of Li–air batteries, are investigated using density functional theory. In the absence of lithium, the most stable surface of b-MnO2, the (110), adsorbs oxygen in the form of peroxo groups bridging between two manganese cations. Conversely, in the absence of excess oxygen, lithium atoms adsorb on the (110) surface at two different sites, which are both tricoordinated to surface oxygen anions, and the adsorption always involves the transfer of one electron from the adatom to one of the five-coordinated manganese cations at the surface, creating (formally) Li+ and Mn3+ species. The co-adsorption of lithium and oxygen leads to the formation of a surface oxide, involving the dissociation of the O2 molecule, where the O adatoms saturate the coordination of surface Mn cations and also bind to the Li adatoms. This process is energetically more favourable than the formation of gas-phase lithium peroxide (Li2O2) monomers, but less favourable than the formation of Li2O2 bulk. These results suggest that the presence of b-MnO2 in the cathode of a nonaqueous Li–O2 battery lowers the energy for the initial reduction of oxygen during cell discharge.

Following the creation of active gold nanocatalysts from phosphine-stabilized molecular clusters

The phosphine-stabilised gold cluster [Au6(Ph2P-o-tolyl)6](NO3)2 is converted into an active nanocatalyst for the oxidation of benzyl alcohol through low-temperature peroxide-assisted removal of the phosphines, avoiding the high-temperature calcination process. The process was monitored using in-situ X-ray absorption spectroscopy, which revealed that after a certain period of the reaction with tertiary butyl hydrogen peroxide, the phosphine ligands are removed to form nanoparticles of gold which matches with the induction period seen in the catalytic reaction. Density functional theory calculations show that the energies required to remove the ligands from the [Au6Ln]2+ increase significantly with successive removal steps, suggesting that the process does not occur at once but sequentially. The calculations also reveal that ligand removal is accompanied by dramatic re-arrangements in the topology of the cluster core.

Phase separation and surface segregation in ceria-zirconia solid solutions

Using a combination of density functional theory calculations and statistical mechanics, we show that a wide range of intermediate compositions of ceria – zirconia solid solutions are thermodynamically metastable with respect to phase separation into Ce-rich and Zr-rich oxides. We estimate that the maximum equilibrium concentration of Zr in CeO2 at 1373 K is ~2%, and therefore equilibrated samples with higher Zr content are expected to exhibit heterogeneity at the atomic scale. We also demonstrate that in the vicinity of the (111) surface, cation redistribution at high temperatures will occur with significant Ce enrichment of the surface, which we attribute to the more covalent character of Zr-O bonds compared to Ce-O bonds. Although the kinetic barriers for cation diffusion normally prevent the decomposition/segregation of ceria-zirconia solid solutions in typical catalytic applications, the separation behaviour described here can be expected to occur in modern three-way catalytic converters, where very high temperatures are reached.

Direct probing of photoinduced electron transfer in a self- assembled biomimetic [2Fe2S]-hydrogenase complex using ultrafast vibrational spectroscopy

A pyridyl-functionalized diiron dithiolate complex, [μ-(4-pyCH2−NMI-S2)Fe2(CO)6] (3, py = pyridine(ligand), NMI = naphthalene monoimide) was synthesized and fully characterized. In the presence of zinc tetraphenylporphyrin (ZnTPP), a self-assembled 3·ZnTPP complex was readily formed in CH2Cl2 by the coordination of the pyridyl nitrogen to the porphyrin zinc center. Ultrafast photoinduced electron transfer from excited ZnTPP to complex 3 in the supramolecular assembly was observed in real time by monitoring the ν(CO) and ν(CO)NMI spectral changes with femtosecond time-resolved infrared (TRIR) spectroscopy. We have confirmed that photoinduced charge separation produced the monoreduced species by comparing the time-resolved IR spectra with the conventional IR spectra of 3•− generated by reversible electrochemical reduction. The lifetimes for the charge separation and charge recombination processes were found to be τCS = 40 ± 3 ps and τCR = 205 ± 14 ps, respectively. The charge recombination is much slower than that in an analogous covalent complex, demonstrating the potential of a supramolecular approach to extend the lifetime of the chargeseparated state in photocatalytic complexes. The observed vibrational frequency shifts provide a very sensitive probe of the delocalization of the electron-spin density over the different parts of the Fe2S2 complex. The TR and spectro-electrochemical IR spectra, electron paramagnetic resonance spectra, and density functional theory calculations all show that the spin density in 3•− is delocalized over the diiron core and the NMI bridge. This delocalization explains why the complex exhibits low catalytic dihydrogen production even though it features a very efficient photoinduced electron transfer. The ultrafast porphyrin-to-NMIS2−Fe2(CO)6 photoinduced electron transfer is the first reported example of a supramolecular Fe2S2-hydrogenase model studied by femtosecond TRIR spectroscopy. Our results show that TRIR spectroscopy is a powerful tool to investigate photoinduced electron transfer in potential dihydrogen-producing catalytic complexes, and that way to optimize their performance by rational approaches.

Spin polarization, orbital occupation and band gap opening in vanadium dioxide: the effect of screened Hartree–Fock exchange

The metal–insulator transition of VO2 so far has evaded an accurate description by density functional theory. The screened hybrid functional of Heyd, Scuseria and Ernzerhof leads to reasonable solutions for both the low-temperature monoclinic and high-temperature rutile phases only if spin polarization is excluded from the calculations. We explore whether a satisfactory agreement with experiment can be achieved by tuning the fraction of Hartree Fock exchange (a) in the density functional. It is found that two branches of locally stable solutions exist for the rutile phase for 12:5% 6 a 6 20%. One is metallic and has the correct stability as compared to the monoclinic phase, the other is insulating with lower energy than the metallic branch. We discuss these observations based on the V 3d orbital occupations and conclude that a ¼ 10% is the best possible choice for spin-polarized VO2 calculations.

Weak intermolecular interactions in an ionically bound molecular adsorbate: cyclopentadienyl=Cu(111)

The dissociative adsorption of cyclopentadiene (C5H6) on Cu(111) yields a cyclopentadienyl (Cp) species with strongly anionic characteristics. The Cp potential energy surface and frictional coupling to the substrate are determined from measurements of dynamics of the molecule together with density functional calculations. The molecule is shown to occupy degenerate threefold adsorption sites and molecular motion is characterized by a low diffusional energy barrier of 40 +/- 3 meV with strong frictional dissipation. Repulsive dipole-dipole interactions are not detected despite charge transfer from substrate to adsorbate.

Mode-specific chemisorption of CH4 on Pt{110}-(1 x 2) explored by first-principles molecular dynamics

The chemisorption of CH4 on Pt{110}-(1 x 2) has been studied by vibrational analysis of the reaction pathway defined by the potential energy surface and, in time reversal, by first-principles molecular dynamics simulations of CH4 associative desorption, with the electronic structure treated explicitly using density functional theory. We find that the symmetric stretch vibration ν1 is strongly coupled to the reaction coordinate; our results therefore provide a firm theoretical basis for recently reported state-resolved reactivity measurements, which show that excitation of the ν1 normal mode is the most efficient way to enhance the reaction probability

Unrestricted Skyrme-tensor time-dependent Hartree-Fock model and its application to the nuclear response from spherical to triaxial nuclei

The nuclear time-dependent Hartree-Fock model formulated in three-dimensional space, based on the full standard Skyrme energy density functional complemented with the tensor force, is presented. Full self-consistency is achieved by the model. The application to the isovector giant dipole resonance is discussed in the linear limit, ranging from spherical nuclei (16O and 120Sn) to systems displaying axial or triaxial deformation (24Mg, 28Si, 178Os, 190W and 238U). Particular attention is paid to the spin-dependent terms from the central sector of the functional, recently included together with the tensor. They turn out to be capable of producing a qualitative change on the strength distribution in this channel. The effect on the deformation properties is also discussed. The quantitative effects on the linear response are small and, overall, the giant dipole energy remains unaffected. Calculations are compared to predictions from the (quasi)-particle random-phase approximation and experimental data where available, finding good agreement

Spontaneous local symmetry breaking: a conformational study of glycine on Cu{311}

Understanding the interplay between intrinsic molecular chirality and chirality of the bonding footprint is crucial in exploiting enantioselectivity at surfaces. As such, achiral glycine and chiral alanine are the most obvious candidates if one is to study this interplay on different surfaces. Here, we have investigated the adsorption of glycine on Cu{311} using reflection-absorption infrared spectroscopy, low-energy electron diffraction, temperature-programmed desorption and first-principles density-functional theory. This combination of techniques has allowed us to accurately identify the molecular conformations present under different conditions, and discuss the overlayer structure in the context of the possible bonding footprints. We have observed coverage-dependent local symmetry breaking, with three-point bonded glycinate moieties forming an achiral arrangement at low coverages, and chirality developing with the presence of two-point bonded moieties at high coverages. Comparison with previous work on the self-assembly of simple amino acids on Cu{311} and the structurally-similar Cu{110} surface has allowed us to rationalise the different conditions necessary for the formation of ordered chiral overlayers.