Interaction between a He atom and a graphite surface

A study is presented of the interaction V(r) between a He atom and a graphite surface. V(r) is assumed equal to a sum of pair interactions U(r ? R_i) between the He and C atoms. None of a set of isotropic potentials (dependent only on the magnitude ¦r ? R_i¦) is consistent with recent scattering data. Anisotropie pair potentials, in contrast, are found to yield good agreement. The origin of this anisotropy is analyzed in terms of the graphite dielectric function and charge density.     

Structures, energetics, and dynamics of helium adsorbed on isolated fullerene ions

Helium adsorbed on C(60)(+) and C(70)(+) exhibits phenomena akin to helium on graphite. Mass spectra suggest that commensurate layers form when all carbon hexagons and pentagons are occupied by one He each, but that the solvation shell does not close until 60 He atoms are adsorbed on C(60)(+), or 62 on C(70)(+). Molecular dynamics simulations of C(60)He(n)(+) at 4 K show that the commensurate phase is solid. Helium added to C(60)He(32)(+) will displace some atoms from pentagonal sites, leading to coexistence of a registered layer of immobile atoms interlaced with a nonregistered layer of mobile atoms.     

Characterization of fluorinated multiwalled carbon nanotubes by x-ray absorption spectroscopy

The C 1s and F 1s x-ray absorption spectra of fluorinated multiwalled carbon nanotubes with different fluorine contents and reference compounds (highly oriented pyrolytic graphite crystals and “white” graphite fluoride) were measured using the equipment of the Russian-German beamline at the BESSY II storage ring with a high energy resolution. The spectra obtained were analyzed with the aim of characterizing multiwalled carbon nanotubes and their products formed upon treatment of the nanotubes with fluorine at a temperature of 420°C. It was established that, within the probing depth (～15 nm) of carbon nanotubes, the process of fluorination occurs uniformly and does not depend on the fluorine concentration. The interaction of fluorine atoms with multiwalled carbon nanotubes in this case proceeds through the covalent attachment of fluorine atoms to graphene layers of the graphite skeleton and is accompanied by a change in the hybridization of the 2s and 2p valence electron states of the carbon atom from the trigonal (sp ²) to tetrahedral (sp ³) hybridization.     

Adsorption and desorption kinetics of Cu and Au on (0001) graphite

The interaction of Au and Cu atoms with the (0001) plane of graphite was studied by mass spectrometric measurements of desorption flux both in the presence and absence of an incident atomic beam. For these systems the condensation coefficient increases from ～0.05 at θ = 0 to unity at θ = 1; furthermore the rate of thermal desorption has a kinetic order of one-half for both systems at low coverage. These observations are consistent with a kinetic model in which two-dimensional nucleation of mobile adsorbed atoms occurs upon adsorption, while the reverse process, loss of atoms from the edges of disc nuclei, is the rate controlling step for desorption. This model implies that bonding of metal atoms to the basal plane of graphite is weak and nonlocalized, with adsorption occurring only when two-dimensional nucleation permits metal-metal bonding.     

C 1s NEXAFS study of rare-earth’s (La,Eu)-graphite intercalation compounds

Electronic structure of unoccupied states of Eu- and thin surface layer of La-intercalation compounds was studied by light polarization dependent NEXAFS at the C 1s threshold in a bulk sensitive (E_kin=1–2 eV) and a more surface sensitive (E_kin=265 eV) partial electron yield mode. It was shown that the C 1s spectra in both cases are mainly characterized by the π*- and σ*-symmetry graphite-derived features. For both systems the π*-derived peak was found at similar energies of exciting photons as for pristine graphite. A decrease of relative intensity of the π*-originated structure in intercalation compounds can be understood by partial occupation of the π*-derived states upon intercalation due to a charge transfer from rare-earth (RE) atoms. NEXAFS features found on both sides of the π* response may be related to pd hybrids forming as a result of chemical interaction between RE atoms and graphite layers.     

Dimensional effects of debye-waller factors in layered crystals

It has been found by He atom scattering and LEED, that the mean square vibrational amplitude 〈u²_c〉 normal to the basal planes of graphite does not saturate at low temperatures to the zero point energy value predicted by Debye theory, but decreases substantially below that value as T approaches zero. This result has been interpreted as being due to the strong anisotropy and reduced dimensionality of graphite, and has been observed, so far, only for surface atoms. Using X-rays, we have observed similar effects for bulk atoms of graphite and 1T-TaS₂. The (00 18) reflection for graphite, and the (00 16) for TaS₂, have been monitored as functions of T between 300 and 5K. While the Debye model works well in both cases above 100K, 〈u²_c〉 saturates to a value 10.2% lower than that predicted by the model in the case of graphite, and 23.8% in the case of TaS₂.     

Influence of the order parameter on the anchoring energy of liquid crystals

No theory of the polar and azimuthal anchoring energies of liquid crystals (LCs) has been developed on a molecular level, despite the scientific and practical topicality of the problem. The interaction energies of mesogenic molecules with graphite and polyethylene surfaces calculated previously by the method of atom-atom potentials are in good agreement with the experimental data, but, at the same time, the calculated polar and azimuthal anchoring energies are larger than their experimental values by one and two orders of magnitude, respectively. To explain these values, the anchoring energy has been assumed to depend not only on the interaction with the surface but also on the interaction between the LC molecules arranged in the model in the form of quasi-layers. The mesogenic molecules have been modeled by rods with virtual C’ atoms (carbon atoms with hydrogen atoms attached to them) “threaded” on them. The molecule orientation has been specified by the polar and azimuthal angles θ _i , φ _i and θ _j , φ _j relative to the directors of the ith and jth layers. The derived polar and azimuthal anchoring energies as well as their dependences on the order parameter have turned out to be close to the experimental data.     

Spectral anomalies of the light-induced drift of rubidium atoms caused by the velocity dependence of transport collision frequencies

The spectral features of the light-induced drift (LID) velocity for rubidium atoms (⁸⁵Rb and ⁸⁷Rb) in an argon buffer medium and in binary buffer mixtures of noble gases (Ne + Ar, Ne + Kr, Ne + Xe, He + Ar, He + Kr, and He + Xe) have been investigated theoretically. A strong temperature dependence of the spectral shape of the LID signal for Rb atoms in an Ar atmosphere is predicted in the temperature range 450 K < T < 800 K. It is shown that the anomalous LID of Rb atoms in binary buffer mixtures of noble gases can be observed at almost any temperature (including the room one) depending on the fractions of neon or helium in these mixtures. The results obtained enable a highly accurate testing of the interatomic interaction potentials used to calculate the drift velocity for anomalous LID in LID experiments.     

In situ Mössbauer spectroscopic study of iron III chloride intercalated in graphite under reaction conditions

In situ⁵⁷Mössbauer spectroscopy has been used to study the process of reduction and Fischer-Tropsch reactions on FeCl₃ intercalated in graphite layers. It is found that on flowing H₂ on graphite intercalated by FeCl₃ at 400° C, FeCl₃ converts to FeCl₂ and partly to small particles of α-Fe. The Mössbauer spectra of the reduced sample are superposition of a sextuplet and two quadrupole doublets indicative of metallic iron and two species of FeCl₂. However, at room temperature and at 400° C for a short period of reduction the magnetic hyperfine splittings (ca. 295 kOe and 262 kOe respectively) are smaller than the corresponding parameters for bulk metallic iron. The differences have been attributed to the interaction between the monolayers of iron atoms and the carbon nets of the graphite support. When the reduction was carried out for a longer period, α-Fe was formed. When a sample reduced for a short period of time is heated at 400°C in the presence of the synthesis gas, part of the iron particles sinter, and α-iron is observed. On heating the above sample once again at 400°C in the presence of the synthesis gas, the remaining small particles of iron are totally converted to the bulk phase (α-Fe). Experimental observations indicate that α-Fe and FeCl₂ are present on the surface as well as inbetween the intercalated graphite layers.     

Strong lithium-polysulfide anchoring effect of amorphous carbon for lithium–sulfur batteries

Solving the shuttle effect caused by lithium polysulfide (LPS) dissolution is important in lithium−sulfur batteries. The anchoring of LPSs to carbon combined with sulfur is a method of suppressing the shuttle effect. This first-principles study is the first to report that amorphous carbon offers the best ability to anchor LPSs. The adsorption energies of LPSs on amorphous carbon are at least six times higher than those on graphene and at least two times higher than those on pyridinic-N doped graphene. The LPSs adsorbed on amorphous carbon undergo significant molecular distortion and/or partial dissociation due to the S-to-C electron transfer of 1.2–1.8 e per molecule, as well as the formation of strong bonds between both the Li and S atoms and the sp- and sp²-site C atoms. We propose an amorphous carbon−graphite hybrid anchoring material, because amorphous carbon can strongly capture LPSs and graphite can act as an electron channel.     

Mössbauer and X-ray studies of Fe-powder mechanically alloyed with C using power ultrasonics

The M?ssbauer and X-rays analysis of as-received Fe-powder and Fe-powder mechanically alloyed with C using high power ultrasonics were carried out. The powder blend of Fe-powder and graphite was processed in He environment during 5 to 50 h. The dissolution of carbon in iron particles and inhomogeneous distribution of C atoms in crystallites was revealed. The ultrasonic milling of the f.c.c. Fe-Ni-powder with graphite was carried out. As established, the saturation of iron particles with carbon under ultrasonic milling occurs for much shorter time as compared to the high-energy ball milling.     

Liquid 3He droplets: Energy systematics and magic numbers

Ground state properties of ³He clusters are investigated in the framework of the Hartree-Fock theory using an effective interaction of phenomenological type. Binding energies and density distributions are evaluated for clusters up to N = 168 atoms. The analysis yields magic number effects at N = 40 and 70. The method predicts the existence of a minimum number of particles forming a bound droplet around N = 20.     

Ripening of subsurface amorphous C clusters formed by low energy He ion bombardment of graphite

Surfaces of highly oriented pyrolytic graphite (HOPG) were bombarded with 100 eV and 500 eV He ions at ion doses of a few 10¹⁵ cm² and temperatures ranging from 300 K to 800 K. AFM images were recorded to investigate the topography of the surfaces after ion bombardment. Supplementary electron energy loss (EEL) and thermal desorption (TD) spectra were measured to determine the C sp² fraction of the bombarded surfaces and the amount of trapped He. The temperature at which He ion bombardment was performed had a drastic effect on the surface structure and topography of the targets on the angstrom-scale and micrometer-scale as well. At 300 K, limited defect atom transport revealed an amorphous but relatively flat HOPG surface. Bombardment at 400 K leads to a granular structure of small protrusions in micrometer-scale AFM images, however, without crystalline order on the surface. The protrusions are due to the formation of subsurface clusters of carbon formed by atoms displaced by ion irradiation. Towards higher temperatures during bombardment the clusters agglomerate and cause the surface layers to bend upwards in dome-like shapes. Simultaneously, the microscopic order of the graphite lattice recovers. At 800 K large areas of the top layer retain their order during bombardment, however, a small number of domes indicate that there still exist some subsurface C clusters. The cluster–cluster distance deduced from the dome distribution indicates that the clusters grow through a ripening process. Annealing of graphite at high temperatures subsequent to ion bombardment at low temperatures is much less effective for recovering the surface crystallinity than ion bombardment at high temperature.     

Use of the continued fraction method for the study of adsorption: Hydrogen on graphite

The local densities of states and energies of adsorption of one, two and a monolayer of hydrogen atoms on the (0001) surface of graphite are calculated. A Hückel type Hamiltonian with pi orbitals for the carbon atoms and 1s orbitals for the hydrogens is used. The densities of states are calculated by the continued fraction method, with an enlarged energy band obtained by surrounding graphite with appropriate pseudoatoms, which proved to be a suitable procedure to obtain the bound states.     

The nature of the adsorption bond between graphite islands and iridium surface

To reveal the nature of adsorption bonds between two-dimensional graphite islands and iridium (111) and (100) faces, a study has been made of the adsorption of potassium and cesium atoms on the surface of these systems, using thermal desorption and Auger electron spectroscopy, as well as surface ionization and thermionic emission techniques. The graphite islands are shown to be weakly bound to the iridium substrate by Van der Waals forces. The unsaturated valence bonds at the periphery of the graphite islands are “lowered down” on to the metal. The recess between the graphite layer and the metal is filled by adsorbing particles through defects in the graphite layer. The atoms can penetrate into the recess in two ways: at T > 1000 K directly from the flux incident on the surface, and at T < 1000 K also by migration from the graphite island surface. The adsorption capacity of this state is ～ (2?3) × 10¹⁴cm^-2. Thermal destruction of the islands at T > 1900 K liberates the potassium and cesium atoms from under the graphite islands. Our study suggests that the reason for the “raised” position of the islands lies in the valence bonds of the graphite layer being saturated, the valence bonds of the metal and its crystallographic orientation being less significant. Therefore one may expect the graphite layer to be raised also above other metals as well. The filling by cesium of the recess between the graphite layer and iridium and of the adsorption phase on the graphite surface, does not change the general “graphitic” shape of the carbon Auger peak. This cesium results, however, in a pronounced splitting of the negative spike on the carbon peak (which provides information on its location relative to the graphite layer) indicating the appearance in the valence band of graphite near the Fermi level of two narrow (～ 2?3 eV) regions with an enhanced density of states originating from the presence of the alkali metal.     

Asymptotic interaction between He,H, H2 and a graphite surface

An atom or molecule far from a surface experiences an interaction V ~ ?C₃z^?3, where z is the distance to the surface. We compute the coefficient C₃ for He, H, and H₂ interacting with a graphite surface. The calculation utilizes measured frequency dependent values of the polarizabilities and dielectric function. Comparison is made with C₃ values deduced from surface scattering and adsorption experiments.     

Pressure shift of atomic resonance lines in liquid and solid helium

We show that for atoms trapped in a liquid He matrix the excitation and emission spectra can be quantitatively described by the bubble model which treats the matrix as an incompressible continuous medium. Comparison with experimental results shows that the model also holds for a solid matrix. The model is only valid in the case where the attractive He–He interaction dominates the attractive part of the foreign atom-helium interaction. Its failure in the case of implanted Na atoms is discussed.     

Shadowgraphic and emission imaging spectroscopic studies of the laser ablation of graphite in an Ar gas atmosphere

Laser ablation of graphite in an Ar atmosphere at 560 Torr was done using a nanosecond-pulse Nd:YAG laser (1064 nm) at a fluence of 12 J/cm². Dynamics in the ejection of carbon species and in their confinement near the graphite surface (<1 mm) due to their numerous collisions with Ar atoms were investigated by shadowgraphy, emission imaging, and emission spectroscopy at delay times of 0.01-100 7s following the laser irradiation. A shock wave was generated, and temporally and spatially dependent emissions from Ar⁺ and Ar were observed in addition to those from carbon species (C, C⁺, and C₂) and the Bremsstrahlung radiation from a hot plasma. We suggest that the dissipation of the kinetic and thermal energies of the carbon species, their backward motion, and their collisions with each other lead to the formation of clusters and particles through the interaction with Ar atoms.     

Simulation of Helium Behaviour in Titanium Crystals Using Molecular Dynamics

The behaviour of helium in Ti crystals at 300 K has been investigated by means of the molecular dynamics. The study is focused on the influences of He-Ti interaction on the aggregation of helium atoms in the substrate. When a Born-Mayer potential is used to describe the He-Ti interaction, the He atoms are unable to cluster with each other due to the weak bridge barrier that cannot trap the helium atoms, Whereas using a He-Ti potential that is constructed by fitting the ab initio pairwise He-Ti potential, the clustering of He atoms can be observed. The results indicate that suitable He-Ti potential plays an important role in the formation of He clusters in metals. Moreover, it is noted that the shape of the formed He cluster is irregular, and the produced defect prefers to congregating on one side of the He cluster rather than spreading symmetrically around it.