Molecular simulation of C60 adsorption onto a TiO2 rutile (1 1 0) surface

A Monte Carlo molecular simulation study is presented on the adsorption and growth of C₆₀ films on the surface of the (1 1 0) face of rutile. Simulations are performed for a temperature of 600 K using atomistic models both for the fullerene molecules and the TiO₂ surface. It is found in this work that C₆₀ is adsorbed preferably in an ordered arrangement along the surface depressions over the exposed undercoordinated Ti cations. At low densities adsorption occurs preferably at alternate rows, with locations in consecutive rows being occupied appreciably only at higher C₆₀ densities. At low densities, the fullerene molecules tend to aggregate into islands in the surface plane. Additional layers of C₆₀ form only as the density increases, and do so before a monolayer is completed in all consecutive rows. Full monolayer capacity obtained at the highest densities is about 0.9 C₆₀ molecules per nm², but this is only achieved by completing the packing of molecules in interstices at a slightly upper level. The fraction of the molecules that lie closest to the surface only amounts to 0.6 molecules per nm².     

密度泛函理论计算内掺氢分子富勒烯H2＠C60及其二聚体的几何结构和电子结构

采用密度泛函理论中的广义梯度近似(generalized gradient approximation,简称GGA),对内掺氢分子富勒烯H₂＠C₆₀及其二聚体的几何结构和电子结构进行了计算研究.发现无论是在H₂＠C₆₀单体,还是在其二聚体中,氢倾向以分子形式存在于碳笼中心处,且在室温下氢分子可以做自由旋转.电子结构分析表明,氢分子掺入到C₆₀和C₁₂₀中,仅对距离费米能级以下-8eV至-5eV能级处有一定的贡献,其他能级的分布和能隙几乎没有变化. 关键词： 几何结构 电子结构 密度泛函     

Uptake and Sequestration of Naphthalene and 1,2-Dichlorobenzene by C60

The interactions of common environmental contaminants with C₆₀ have been studied to evaluate the environmental impact of carbon nanomaterials. The adsorption and desorption interaction of the hydrophobic contaminants naphthalene and 1,2-dichlorobenzene with C₆₀ was characterized. Processes that cause the wetting and disaggregating of C₆₀ particles also affect the extent of organic contaminant sorption to C₆₀ aggregates by orders of magnitude. C₆₀ dissolved in organic solvents such as toluene can form stable nanoscale aggregates upon vigorous mixing in water. These nanoscale C₆₀ particles form stable suspensions in water and are referred to as ‘nano-C₆₀’. Desorption of contaminants from stable suspensions of nano-C₆₀ exhibits hysteresis. The experimentally observed adsorption/desorption hysteresis is described by a two-compartment desorption model: first, adsorption to the external surfaces that are in contact with water, and second, adsorption to the internal surfaces within the aggregates.     

Li adsorption on a Fullerene–Single wall carbon nanotube hybrid system: Density functional theory approach

In this study, we investigate Li adsorption mechanisms on the C₆₀-SWCNT hybrid system using density functional theory. It is found that the Li adsorption energy of the C₆₀-SWCNT hybrid system is increased in comparison to that of the pure SWCNT. The Li adsorption energy ranges from −1.917 eV to −2.642 eV for the single-Li adsorbed system and from −2.351 eV to −2.636 eV for the double-Li adsorbed system. It is also found that the adsorption energy becomes similar at most positions throughout the structure. In addition, the Li adsorption energy of 31-Li system is calculated to be −1.863 eV, which is significantly lower than the Li–Li binding energy (−1.030 eV). These results infer that Li atoms will be adsorbed on the space 1) between C₆₀ and C₆₀; 2) between SWCNT and C₆₀; 3) the rest of the space (e.g. between SWCNTs), rather than form Li clusters. As more Li atoms are adsorbed onto the C₆₀-SWCNT hybrid system due to such improved Li adsorption capability, the metallic character of the system is enhanced, which is confirmed via the band structure and electronic density of states.     

Fullerene-C60 and crown ether doped on C60 sensors for high sensitive detection of alkali and alkaline earth cations

Fullerenes are effective acceptor components with high electron affinity for charge transfer. The significant influences of chemical adsorption of the cations on the electrical sensitivity of pristine C₆₀ and 15-(C₂H₄O)₅/C₆₀ nanocages could be the basis of new generation of electronic sensor design. The density functional theory calculation for alkali and alkaline earth cations detection by pristine C₆₀ and 15-(C₂H₄O)₅/C₆₀ nanocages are considered at B3LYP level of theory with 6–31 G(d) basis set. The quantum theory of atoms in molecules analysis have been performed to understand the nature of intermolecular interactions between the cations and nanocages. Also, the natural bond orbital analysis have been performed to assess the intermolecular interactions in detail. Furthermore, the frontier molecular orbital, energy gap, work function, electronegativity, number of transferred electron (∆N), dipole moment as well as the related chemical hardness and softness are investigated and calculated in this study. The results show that the adsorption of cations (M=Na⁺, K⁺, Mg²⁺ and Ca²⁺) are exothermic and the binding energy in pristine C₆₀ nanocage and 15-(C₂H₄O)₅/C₆₀ increases with respect to the cations charge. The results also denote a decrease in the energy gap and an increase in the electrical conductivity upon the adsorption process. In order to validate the obtained results, the density of state calculations are employed and presented in the end as well.     

Organizing C60 molecules on a nanostructured Au(111) surface

We have studied, using scanning tunneling microscopy, the adsorption of C₆₀ molecules on a nanostructured Au(111) surface consisting of artificially created two-dimensional cavities. These cavities, one atomic layer deep, are found to be effective as molecular traps at room temperature. Gold atoms at step edges are found to respond to the adsorption of C₆₀ molecules and gross faceting is observed for steps connected with R30° oriented C₆₀ molecular islands. Structural models are proposed to establish the step structures related to all three types of molecular islands.     

Ab initio calculations of supramolecular complexes of fullerene C60 with CdTe and CdS

This paper presents the results of ab initio quantum-chemical calculations of supramolecular complexes C₆₀CdHal, [C₆₀]₄CdHal, and [C₆₀]₆CdHal (Hal = S, Te), which simulate the defects forming in fullerite during the absorption or adsorption of cadmium telluride (sulfide). Calculations of the electronic structure of complexes with inclusion of their relaxation to the equilibrium state have been performed in terms of the density functional theory with the B3LYP hybrid functional. The obtained enthalpies of formation of complexes show that their formation leads to the energy gain of the order of 0.5–1.5 eV depending on the complex type. It has been shown that the formation of tetrahedral complexes [C₆₀]₄CdTe with the intercalated CdTe molecule is possible only with a considerable distortion of the tetrahedral void. The energy spectrum of low-lying excited electron states for the linear and octahedral complexes has been calculated. It has been found that a decrease in symmetry with the formation of complexes leads to the appearance of excited states of allowed singlet transitions in the electron spectrum, which are forbidden in optical spectra of initial components.     

C60富勒烯-巴比妥酸及其二聚体几何结构和电子结构的密度泛函计算研究

采用基于密度泛函理论的广义梯度近似,对C₆₀富勒烯-巴比妥酸及其二聚体的几何结构和电子结构进行了计算研究.发现：C₆₀富勒烯-巴比妥酸只有一种稳定结构,且掺杂巴比妥酸基团对C₆₀分子构型的影响是局域的.C₆₀富勒烯-巴比妥酸的二聚体有三种同素异构体,分别以［6,5］—［6,5］,［6,6］—［6,5］和［6,6］—［6,6］三种方式键合,从能隙大小顺序和总能相对大小来看,［6,6］—［6,6］结构最为稳定.电子结构方面,在C₆₀富勒烯-巴比妥酸单体中,Donor-Acceptor电荷转移体系为C₆₀富勒烯-巴比妥酸,即电荷是从C₆₀向巴比妥酸转移.由前线轨道和自旋布居数得知,C₆₀富勒烯-巴比妥酸单体很好地保留了C₆₀的电磁性质,但稳定性下降,易发生二次加成反应形成二聚体.对于C₆₀富勒烯-巴比妥酸二聚体,Mulliken电荷分析显示,在加成四元环处的碳原子分别得到0104e和0106e电荷,而与它们邻近的碳原子则失去电子,带有正电荷,且距加成位置越近的碳原子失去的电荷越多.在远离加成位置处,碳原子的净电荷变化相对较小.与单体152eV能隙相比,二聚体中的能隙为1.45eV.其前线轨道分布与单体相比,最高占据轨道几乎未变,但最低未占据轨道发生了很大变化. 关键词： 几何结构 电子结构 密度泛函     

Investigations on the behaviour of C60 as a resist in X-ray lithography

Oxygen-free C₆₀ films on various substrates have been used as negative resist in X-ray lithography, yielding pure-carbon microstructures of good quality via synchrotron irradiation through an X-ray mask and subsequent development. While X-ray s induce the polymerization of C₆₀ into insoluble product, large numbers of secondary electrons backscattered from the substrate inhibit this, which we attribute to the different cross sections of X-ray s and electrons in C₆₀. Both electrons and X-ray s generate neutral electronically excited C₆₀ molecules. At a low density of excited C₆₀, as generated by X-ray s, they react predominantly with neighbouring molecules in their ground state via a 2+2-cycloaddition similar to UV polymerization. At a high density of excited C₆₀, as generated by secondary electrons, the excited molecules are not able to react with each other due to orbital symmetry. Instead, the excited states quench each other, thus inhibiting the polymerization. The reduction of the resolution in the C₆₀ pattern, and the inhibition of the polymerization near the interface through backscattered electrons, can be reduced by using substrate materials from which only few electrons emerge. To maintain the density of excited C₆₀ molecules at the interface below the point where the quenching reaction prevails, low synchrotron-radiation intensities are recommended. PACS 81.05.Tp; 82.50.-m; 85.40.Hp     

Bucky-corn: van der Waals composite of carbon nanotube coated by fullerenes

ABSTRACT

Can a C₆₀ layer cover a surface of single-wall carbon nanotube (SWCNT) forming an exohedral pure-carbon hybrid with only van der Waals interactions? The aim of the present paper is to address this question and to demonstrate that the fullerene shell layer in such a bucky-corn structure can be stable. Theoretical study of the structure, stability and electronic properties of bucky-corn hybrids is reported for the shell of C₆₀ and C₇₀ molecules on an individual SWCNT, C₆₀ dimers on an individual SWCNT as well as C₆₀ molecules on SWNT bundles. The geometry and total energies of the bucky-corn hybrids were calculated by the molecular dynamics method, while the density functional theory method was used to simulate the electronic band structures.     

Simulation of the structure and electronic configuration of Pdn(C60)m complexes

The structure and electronic configuration of Pd(C₆₀)₂, Pd₂(C₆₀)₂, Pd₃(C₆₀)₃, and Pd₆(C₆₀)₃ complexes have been simulated in terms of the density functional theory within the Perdew—Burke—Ernzerhof (PBE) approximation. The results of the calculation of the Pd₆(C₆₀)₃ trimer have been used to simulate the structure of the quasi-one-dimensional polymer [C₆₀Pd₃]_n molecule. For this macromolecule, the oneelectron energy levels have been calculated. It has been found that the band gap is 0.6 eV. The calculations have been performed using the crystal orbital method in the extended Hückel approximation. The possibility of using the obtained results for evaluating the catalytic properties of the studied complexes has been discussed.     

Ab initio calculation of the electronic and vibrational properties of metal‐organic molecules based on cyclic C6 intercalated with some group VIII transition metals

The vibrational and electronic properties of a new class of organometallic sandwich molecules, (C₆)_nMe_n‐1, based on stacks of cyclic C₆ intercalated with Fe and Ru have been studied using first principles density functional techniques (DFT). Spectral properties as well as the HOMO‐LUMO gap energy in molecules containing up to eight C₆ layers have been calculated. The HOMO‐LUMO energy gap in these molecules is < 1 eV and decreases significantly in longer molecules. It is shown that infinite chains should have excellent metallic properties. These molecules are promising for nanoelectronic applications, due to their predicted high stability, conductivity, and magnetic properties.     

Comparative study of optical parameters of fullerene C60 film at different temperatures

Fullerene C₆₀ thin films on glass substrate (around 2000 ? thickness) were prepared by thermal evaporation technique. The structural, surface morphology and optical properties of the films were studied. The optical properties of fullerene C₆₀ were investigated in the spectral range 200 nm to 900 nm using a UV-Vis spectrophotometer at room temperature as well as at liquid nitrogen temperature (77 K). The optical band gap at room temperature is found to be 2.30 eV, which gradually decreases with lowering the temperature and reaches to 2.27 at 77 K. The thickness and refractive index of fullerene C₆₀ film were calculated by ellipsometry. From the X-ray analysis, we have calculated the grain size, dislocation density, number of crystallite per unit area, and strain of the film at room temperature. The surface morphology of film was analyzed by scanning electron microscope (SEM). The present result show that the fullerene C₆₀ film becomes more conducting at low temperature.     

A first-principles study on the adsorption behaviour of methanol and ethanol over C59B heterofullerene

In the present study, the adsorption behaviour of methanol (CH₃OH) and ethanol (C₂H₅OH) molecules over heterofullerene C₅₉B surface is studied by density functional theory calculations. This heterofullerene is obtained from C₆₀ by substituting a carbon atom with a boron atom and relaxing self-consistently the structure to the local minimum. The adsorption of CH₃OH and C₂H₅OH on the C₅₉B is exothermic and the relaxed geometries are stable. The CH₃OH and C₂H₅OH adsorption can also induce a change in the highest occupied molecular orbital and the lowest unoccupied molecular orbital energy gap of the nanocage. The dehydrogenation pathways of CH₃OH and C₂H₅OH via O–H and C–H bonds scission are also examined. The results indicate that O–H bond scission is the most favourable pathway on the C₅₉B surface.     

Hydrogen migration on the C60 fullerene

We investigate the migration barriers, transition states, and optimum migration paths of hydrogen on the C₆₀ fullerene using the ab initio density functional theory. Calculated energy barriers tend to be higher for non-local exchange-correlation functionals. We find that the migration between adsorption sites with the same energy has high migration barriers, and thus the initial stages of the H nucleation requires desorption–adsorption cycles. The migration barrier is reduced near another H adsorbate. The migration may be involved more in the later stages of the regio-selective hydrogenation of C₆₀. We find that the migration barriers are reduced by the presence of hydrogen sources, and the hydrogenating agents in the environment are required in order to reach the regio-selective hydrogenation of the C₆₀ fullerene.     

Structural, electronic and magnetic properties of Fen@C60 and Fen@C80 (n=2-7) endohedral metallofullerene nano-cages: First principles study

We studied the structural, electronic and magnetic properties of small Fe_n clusters (n=2-7) endohedrally doped in icosahedral C₆₀ and C₈₀ fullerenes using first principles calculations based on the density functional theory. It is found that the encapsulated Fe_n clusters inside icosahedral C₈₀ are energetically favorable while Fe_n@C₆₀ metallofullerene nano-cages are not. The binding energies of the Fe_n encapsulated in C₆₀ are positive and increase with the number of iron atoms (n) while those of the Fe_n@C₈₀ are negative and their absolute values increase up to n=6. The encapsulation does not significantly change the enclosed cluster structure, but the total magnetic moment of the larger clusters reduces due to a stronger Fe-C hybridization.     

B-, N-doped and BN codoped C60 heterofullerenes for environmental monitoring of NO and NO2: a DFT study

ABSTRACT

Using density functional theory calculations, we investigate the gas sensing performance of B-, N-doped and BN-codoped C₆₀ fullerenes towards NO and NO₂ molecules. The calculated adsorption energies and net charge-transfer values indicate that NO and NO₂ molecules have a stronger interaction with the BN-codoped fullerenes compared to the B- or N-doped ones. It is also found that the electronic properties of the BN-codoped C₆₀ exhibit a larger sensitivity towards NO and NO₂ molecules. An increase in the concentration of doped/co-doped B and N atoms tends to weaken the gas sensing ability of these systems.     

Use of surface acoustic waves for analysis of gases and surface processes induced by them

An analytical expression for the magnitude of the “response” of surface acoustic waves (SAWs) to gases is obtained. It is tested experimentally. The main features of the detection of gases by means of SAWs are predicted theoretically and confirmed experimentally. The SAWs in coated and uncoated gas sensors are compared. A technique for using SAWs to determine the relative changes in the density (Δρ/ρ) and the elastic moduli (ΔC ₁₁/C ₁₁ and ΔC ₄₄/C ₄₄) of films upon the adsorption (desorption) of gases is proposed. The possibility of using this technique to analyze adsorption and desorption processes is demonstrated. The adsorption properties of polycrystalline, thermally deposited palladium films before and after low-temperature vacuum annealing, as well as unannealed Pd and Pd:Ni films, are compared. The prospects of using SAWs to detect gases and to study surface processes induced by them are discussed. Zh. Tekh. Fiz. 68, 73–81 (February 1998)     

Impact of a physiological medium on the aggregation state of C<Subscript>60</Subscript> and C<Subscript>70</Subscript> fullerenes

The C₆₀ and C₇₀ fullerene-cluster size distribution in aqueous solutions and a physiological medium is studied via dynamic light scattering. The initial aqueous solutions of fullerenes obtained via different methods are found to contain clusters with a characteristic size of about 100 nm. The additional aggregation of fullerenes is observed after their transfer into a physiological medium (0.9% NaCl) and is established to depend on the preparation method. The cluster-size distribution in a fullerene–pectic-acid mixture is found to vary in water and a physiological medium. The results reveal the need for additional studies of the structure and properties of C₆₀ and C₇₀ molecules, as well as their complexes with medicines, in a physiological medium for medical applications.     

Modulation of the work function of fullerenes C60 and C70 by alkali-metal adsorption: A theoretical study

The impact of alkali-metal (Li/Na/Cs) adsorption on work function of fullerenes C₆₀ and C₇₀ was investigated by first-principles calculations. After adsorption, the work functions of fullerenes C₆₀ and C₇₀ decrease distinctly and vary linearly with the electronegativity of the alkali metal elements, and the positions where the alkali atoms are adsorbed considerably influence the work functions. On the contrary, a vacancy defect elevates the work functions of the fullerenes C₆₀ and C₇₀. The variation in the work functions rests with variation in Fermi level (which are attributed to charge transfer) and variation in vacuum levels (which are attributed to the induced dipole moments). Moreover, alkali-metal adsorption can also improve the electric conductivity of a fullerene mixture of C₆₀ and C₇₀.