Highly Stable [C60AuC60]+/- Dumbbells.

Ionic complexes between gold and C60 have been observed for the first time. Cations and anions of the type [Au(C60)2]+/- are shown to have particular stability. Calculations suggest that these ions adopt a C60-Au-C60 sandwich-like (dumbbell) structure, which is reminiscent of [XAuX]+/- ions previously observed for much smaller ligands. The [Au(C60)2]+/- ions can be regarded as Au(I) complexes, regardless of whether the net charge is positive or negative, but in both cases, the charge transfer between the Au and C60 is incomplete, most likely because of a covalent contribution to the Au-C60 binding. The C60-Au-C60 dumbbell structure represents a new architecture in fullerene chemistry that might be replicable in synthetic nanostructures.

Strained zigzag graphene nanoribbon devices with vacancies as perfect spin filters.

The transport properties of zigzag graphene nanoribbons (zGNRs) were studied by density functional theory (DFT) in conjunction with Green's function analysis. In particular, spin transport through a zGNR (12,0) device was investigated under the constraint of ferromagnetic coordination of the ribbon edges. Several configurations with two vacant sites in the edge and the bulk region of the zGNR device were derived from this system. For all structures, magnetocurrent ratios (MCRs) were recorded as a function of the bias as well as the amount of strain applied longitudinally to the devices. ZGNR devices with vacancies in the edge regime turn out to exhibit perfect spin-filter activity for well-defined choices of the strain and the bias, carrying completely polarized minority spin currents. In the alternative structure, characterized by vacancies in the bulk regime, spin currents with majority orientation prevail. With respect to both the sign and the size, the MCR is seen to depend sensitively on the device parameters, i.e., the vacancy locations, the bias, and the amount of strain. These results are interpreted in terms of density-of-states distributions, transmission spectra, and transmission operator eigenstates.

Vacancy patterning and patterning vacancies: controlled self-assembly of fullerenes on metal surfaces.

A density functional theory study accounting for van der Waals interactions reveals the potential of metal surface vacancies as anchor points for the construction of user-defined 2D patterns of adsorbate molecules via a controlled self-assembly process. Vice versa, energetic criteria indicate the formation of regular adsorbate-induced vacancies after adsorbate self-assembly on clean surfaces. These processes are exemplified by adsorbing C60 fullerene on Al(111), Au(111), and Be(0001) surfaces with and without single, triple, and septuple atom pits. An analysis of vacancy-adatom formation energetics precedes the study of the adsorption processes.

Ordered phases of ethylene adsorbed on charged fullerenes and their aggregates.

In spite of extensive investigations of ethylene adsorbed on graphite, bundles of nanotubes, and crystals of fullerenes, little is known about the existence of commensurate phases; they have escaped detection in almost all previous work. Here we present a combined experimental and theoretical study of ethylene adsorbed on free C60 and its aggregates. The ion yield of [Formula: see text] measured by mass spectrometry reveals a propensity to form a structurally ordered phase on monomers, dimers and trimers of C60 in which all sterically accessible hollow sites over carbon rings are occupied. Presumably the enhancement of the corrugation by the curvature of the fullerene surface favors this phase which is akin to a hypothetical 1 × 1 phase on graphite. Experimental data also reveal the number of molecules in groove sites of the C60 dimer through tetramer. The identity of the sites, adsorption energies and orientations of the adsorbed molecules are determined by molecular dynamics calculations based on quantum chemical potentials, as well as density functional theory. The decrease in orientational order with increasing temperature is also explored in the simulations whereas in the experiment it is impossible to vary the temperature.

Impact of tube curvature on the ground-state magnetism of axially confined single-walled carbon nanotubes of the zigzag-type.

The magnetic properties of axially confined, hydrogenated single-walled carbon nanotubes (SWCNTs) of the (n,0)-type with n=5-24 are systematically explored by density functional theory. Emphasis is placed on the relation between the ground-state magnetic moments of SWCNTs and zigzag graphene nanoribbons (ZGNRs). Comparison between the SWCNTs considered here and ZGNRs of equal length gives rise to two basic questions: 1) how does the nanotube curvature affect the antiferromagnetic order known to prevail for ZGNRs, and 2) to what extent do the magnetic moments localized at the SWCNT edges deviate from the zero-curvature limit of n/3µB ? In response to these questions, it is found that systems with n≥7 display preference for antiferromagnetic order at any length investigated, whereas for n=5, 6 the magnetic phase varies with tube length. Furthermore, elementary patterns are identified that describe the progression of the magnitude of the magnetic moment with n for the longest tubes explored in this work. The spin densities of the considered SWCNTs are analyzed as a function of the tube length L, with L ranging from 3 to 11 transpolyene rings for n≥7 and from 3 to 30 rings for n=5 and 6.

Theoretical investigation into the structural, thermochemical, and electronic properties of the decathio[10]circulene.

For the first time, a theoretical study has been performed on the prototypical decathio[10]circulene (C(20)S(10)) species, which is an analogue of the novel octathio[8]circulene "Sulflower" molecule (C(16)S(8)). Examinations of the singlet and triplet states of C(20)S(10) were made at the B3LYP/6-311G(d) level. Local minima of C(2) and C(s) symmetry were found for the lowest singlet and triplet states, respectively. The stability of C(20)S(10) was assessed by calculating the ΔH°(f) of C(16)S(8) and C(20)S(10) and the ΔH(o) for their decomposition into C(2)S units. Frontier molecular orbital plots show that structural adjacent steric factors along with the twist and strain orientations of C(20)S(10) do not disturb the aromatic π-delocalizing effects. In fact, C(20)S(10) maintains the same p(z) HOMO character as C(16)S(8). These similarities are further verified by density-of-states characterization. Calculated infrared spectra of C(16)S(8) and C(20)S(10) show broad similarities. Molecular electrostatic potential results reveal that eight of the peripheral sulfur atoms are the most electronegative atoms in the molecule, while the interior ten-membered ring exhibits virtually no electronegativity.

Chemistry in acetone complexes of metal dications: a remarkable ethylene production pathway.

Electrospray ionization can generate microsolvated multiply charged metal ions for various metals and ligands, allowing exploration of chemistry within such clusters. The finite size of these systems permits comparing experimental results with accurate calculations, creating a natural laboratory to research ion solvation. Mass spectrometry has provided much insight into the stability and dissociation of ligated metal cations. While solvated singly charged ions tend to shrink by ligand evaporation, solvated polycations below a certain size exhibit charge reduction and/or ligand fragmentation due to organometallic reactions. Here we investigate the acetone complexes of representative divalent metals (Ca, Mn, Co, Ni, and Cu), comparing the results of collision-induced dissociation with the predictions of density functional theory. As for other solvated dications, channels involving proton or electron transfer compete with ligand loss and become dominant for smaller complexes. The heterolytic C-C bond cleavage is common, like in DMSO and acetonitrile complexes. Of primary interest is the unanticipated neutral ethylene loss, found for all metals studied except Cu and particularly intense for Ca and Mn. We focus on understanding that process in the context of competing dissociation pathways, as a function of metal identity and number of ligands. According to first-principles modeling, ethylene elimination proceeds along a complex path involving two intermediates. These results suggest that chemistry in microsolvated multiply charged ions may still hold major surprises.

Do methanethiol adsorbates on the Au(111) surface dissociate?

The interaction of methanethiol molecules CH3SH with the Au(111) surface is investigated, and it is found for the first time that the S-H bond remains intact when the methanethiol molecules are adsorbed on the regular Au(111) surface. However, it breaks if defects are present in the Au(111) surface. At low coverage, the fcc region is favored for S atom adsorption, but at saturated coverage the adsorption energies at various sites are almost isoenergetic. The presented calculations show that a methanethiol layer on the regular Au(111) surface does not dimerize.

Equilibrium geometries and associated energetic properties of mixed metal-silicon clusters from global optimization.

The structural properties of the cluster series Me(m)Si(7-m) (Me = Cu and Li, m < or = 6) are studied by density functional theory (DFT) employing a plane wave basis. The equilibrium geometries and energetic properties of these clusters are obtained by use of the simulated annealing procedure in conjunction with the Nosé thermostat algorithm. The lowest energy isomer thus obtained is analyzed by density functional theory at the B3LYP/6-311+G(d,p) level including all electrons. Pentagonal ground state structures derived from the D(5)(h) equilibrium geometries of both Si(7) and Cu(7) are obtained for Cu(m)Si(7-m) with m < 6. The Li(m)Si(7-m) clusters, in contrast, tend toward adsorption geometries where m Li atoms are attached to a Si(7-m)framework with pronounced negative charge. For both Li(m)Si(7-m) and Cu(m)Si(7-m), a marked decrease of the energy gap is found as the number of metal atom constituents increases.

Ne2+[II (1/2)u]: radiative decay and electronic predissociation.

Metastable fragmentation of neon dimer ions has been investigated by measuring and analyzing high resolution kinetic energy release distributions. Data were obtained by a modified MIKE (mass-analyzed ion kinetic energy) scan technique. Due to the high energy resolution it was possible to distinguish two different reaction mechanisms in the micros time regime which produce Ne+ ions with different kinetic energy distributions. Theoretical studies based on ab initio calculations of potential energy curves allowed the assignment of the reactions to specific electronic transitions in the excited Ne2+ ion. The unusual bimodal kinetic energy release distribution arises from competition between radiative and non radiative decay of the long-lived Ne2+ II(1/2)u state.

Comparative investigation on non-IPR C68 and IPR C78 fullerenes encaging Sc3N molecules.

A computational study on the experimentally detected Sc(3)N@C(68) cluster is reported, involving quantum chemical analysis at the B3LYP/6-31G level. Extensive computations were carried out on the pure C(68) cage which does not conform with the isolated pentagon rule (IPR). The two maximally stable C(68) isomers were selected as initial Sc(3)N@C(68) cage structures. Full geometry optimization leads to a confirmation of an earlier assessment of the Sc(3)N@C(68) equilibrium geometry (Nature 2000, 408, 427), namely an eclipsed arrangement of Sc(3)N in the C(68) 6140 frame, where each Sc atom interacts with one pentagon pair. From a variety of theoretical procedures, a D(3h) structure is proposed for the free Sc(3)N molecule. Encapsulated into the C(68) enclosure, this unit is strongly stabilized with respect to rotation within the cage. The complexation energy of Sc(3)N@C(68) cage is found to be in the order of that determined for Sc(3)N@C(80) and exceeding the complexation energy of Sc(3)N@C(78). The cage-core interaction is investigated in terms of electron transfer from the encapsulated trimetallic cluster to the fullerene as well as hybridization between these two subsystems. The stabilization mechanism of Sc(3)N@C(68) is seen to be analogous to that operative in Sc(3)N@C(78). For both cages, C(68) and C(78), inclusion of Sc(3)N induces aromaticity of the cluster as a whole.