Mechanisms of inelastic scattering of low-energy protons by C6H6, C60, C6F12, and C60F48 molecules

The mechanisms of inelastic scattering of low-energy protons with a kinetic energy of 2–7 eV by C₆H₆, C₆F₁₂, C₆₀, and C₆₀F₄₈ molecules are studied using the methods of quantum chemistry and nonempirical molecular dynamics. It is shown that, for the C₆H₆ + proton and C₆₀ + proton systems, starting from a distance of 6 Å from the carbon skeleton, the electronic charge transfer from the aromatic molecule to H⁺ occurs with a probability close to unity and transforms the H⁺ ion into a hydrogen atom and the neutral C₆H₆ and C₆₀ molecules into cation radicals. The mechanism of interaction of low-energy protons with C₆F₁₂ and C₆₀F₄₈ molecules has a substantially different character and can be considered qualitatively as the interaction between a neutral molecule and a point charge. The Coulomb perturbation of the system arising from the interaction of the noncompensated proton charge with the Mulliken charges of fluorine atoms results in an inversion of the energies of the electronic states localized, on the one hand, on the positively charged hydrogen ion and, on the other hand, on the C₆F₁₂ and C₆₀F₄₈ molecules. As a result, the neutral molecule + proton state becomes the ground state. In turn, this inversion makes the electronic charge transfer energetically unfavorable. Quantum-chemical and molecular-dynamics calculations on different levels of theory showed that, for fluorine derivatives of some aromatic structures (C₆F₁₂, C₆₀F₄₈), the barriers to proton penetration through carbon hexagons are two to four times lower than for the corresponding parent systems (C₆H₆, C₆₀). This effect is explained by the absence of active π-electrons in the case of fluorinated molecules.     

A computational study of interplay between hydride bonding and cation–π interactions: H-Mg-H···X···Y triads (X = Li+, Na+, Y = C2H2, C2H4, C6H6) as model systems

In the present study, H-Mg-H···X···Y (X = Li⁺, Na⁺ and Y = C₂H₂, C₂H₄, C₆H₆) triads have been investigated at MP2/6-311++G(2d,2p) computational level to characterise cooperative effects between hydride bonding and cation–π interactions. Molecular geometries, binding energies, cooperative energies and many-body interaction energies were evaluated. The diminutive energy values in triads with Li⁺ are larger than respective values in triads with Na⁺. The electronic properties of the complexes are analysed using parameters derived from the quantum theory of atoms in molecules methodology.     

C80H80几何结构和电子性质的密度泛函研究

采用密度泛函理论方法中的广义梯度近似,对C₈₀H₈₀几何结构和电子性质进行了研究. 几何结构研究表明:在C₈₀H₈₀可能稳定存在的两种同分异构体中, 连接12个五边形的20个C原子内部氢化,其余60个C原子外部氢化所形成的结构即 H₂₀@C₈₀H₆₀最稳定,其仍然保持I_h对称性. 通过对H₂₀@C₈₀H₆₀的能级、前线轨道和态密度分析可知: 在H₂₀@C₈₀H₆₀中, H原子的原子轨道与C原子的原子轨道之间在占据态轨道上有较强的杂化, H原子对H₂₀@C₈₀H₆₀的占据态轨道的贡献比较大. 其最高占据轨道主要由外部H原子和碳笼来贡献,而最低未占据轨道主要由内部H原子贡献, 表明内外H原子在H₂₀@C₈₀H₆₀的化学反应中承担不同的角色. H₂₀@C₈₀H₆₀为闭壳层结构,所有电子都是配对的,表现为非磁性.     

Theoretical insights into the host–guest interactions between [6]cycloparaphenyleneacetylene and its anthracene‐containing derivative and fullerene C70

The host–guest complexes formed with [6]cycloparaphenyleneacetylene ([6]CPPA) and its anthracene‐containing derivative ([6]CPPAs) hosts and fullerene C₇₀ guest were explored by density functional calculations. Besides two previously reported configurations in which C₇₀ guest is standing or lying in the cavity of the host, we found a new kind of configuration in which C₇₀ guest is half‐lying in the cavity of the host. More interestingly, the calculated results revealed that the fine‐tuning deformations occur readily during the formations of the complexes, suggesting that both [6]CPPA and [6]CPPAs are highly elastic host molecules. The large host–guest binding energies indicate that both two host molecules, [6]CPPA and [6]CPPAs, have excellent encapsulation ability for C₇₀ guest, and the [6]CPPAs even has much better encapsulation ability for C₇₀ than [6]CPPA. Furthermore, the host–guest interactions regions were detected and visualized in real space based on the electron density and reduced density gradient. Additionally, ¹H NMR spectra of those three different kinds of configurations mentioned earlier have been calculated with gage‐independent atomic orbital method, which may be helpful for further experimental characterizations in future. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

Atomic-core dynamics and the electronic structure of some endo-and exohedral complexes of fullerenes with light elements

The atomic and electronic structure of some endo-, exo-, and endo-exohedral complexes of the fullerene C₆₀ with various guest atoms and molecules (He_n, H₂, and Li₂) are investigated using semiempirical and nonempirical quantum-chemical methods. The atomic core dynamics is studied by the method of molecular dynamics. It is shown that guest atoms and molecules in fullerene polyhedra acquire an orbital angular momentum due to the correlated motion of nuclei above the low-energy barriers of the potential surface within the carbon polyhedron even at low temperatures (from 4 to 78 K). The emergence of orbital angular momenta of nuclei of guest atoms and molecules is attributed to a change in the contribution of the orbital angular momentum of electrons to the potential surface of the complexes. The motion of Li ions in a polyhedron leads to blurring of the top of the valence band and to the emergence of a charge polarization wave in the carbon polyhedron.     

Hyperfine and magnetic properties of 19e− (electron reservoir) sandwiches of Fe(I), C5R5FeC6R6 (where R=H or CH3) and (C6(CH3)6)2Fe+: Mössbauer experiments and molecular orbital calculations

The four compounds C₅H₅FeC₆H₆, C₅H₅Fe(CH₃₎₆, C₅(CH₃₎₅FeC₆(CH₃₎₆ and (C₆(CH₃₎₆₎₂Fe⁺ were studied by Mössbauer spectroscopy on powders. On the basis of semi-empirical molecular orbital calculation (Iterative Extended Hückel with self-consistence of the charge) in which parameters derived from X-ray data are used, we have modelized the thermal behaviour of the electric field gradient (EFG) tensor from 4 K to 300 K. The reduction in magnitude of electronic observables (e.g. spin orbit coupling constant and EFG magnitude) gave evidence for a dynamic Jahn-Teller effect. Spectra in a high magnetic field (6 teslas) confirmed the paramagnetic behaviour of the compounds. The sign of the EFG tensor, the magnetic hyperfine field tensor and its orientation with respect to the EFG tensor were determined.     

Adsorption of ethylene on clean and oxygen precovered Cu(110) surfaces

UV photoemission spectroscopy (UPS) with He I and He II radiation is used to study the interaction of C₂H₄ with clean and oxygen precovered Cu(110) surfaces at 90 K. On the clean surface only-bonding of the C₂H₄ molecules is observed whereas preadsorbed oxygen causes a second molecular orbital to be involved in the chemisorption. This result is consistent with the differing behaviour of the work function change during thermal desorption of C₂H₄.     

富勒烯C20分子器件的电子结构和传导特性

运用基于密度泛函理论和基于非平衡格林函数的第一性原理方法研究了富勒烯C₂₀分子及连接电极构成的C₂₀分子器件的电子结构及电子输运性质.构建了三个基于C₂₀分子的嵌入K和Si原子的电子输运系统,并得到了电子透射谱和分子轨道分布.分析了三种器件的电子结构和输运性质的产生原因,说明C₂₀分子器件的电子传导主要集中在外壳.在C₂₀分子空笼中嵌入K和Si原子后,其电子输运仍然主要集中于富勒烯C₂₀的外壳. 关键词： 20分子')" href="#">富勒烯C₂₀分子 电子结构 电子传导     

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.     

碳链输运对基团吸附的敏感性分析

基于局域原子轨道的密度泛函理论和非平衡格林函数方法,研究了碳链输运特性对分别吸附7种常见官能团NO₂, CN, CHO, Br, C₆H₅, C₅H₄N和NH₂时的敏感性. 计算表明,电流对C₆H₅和CHO的吸附最为敏感,其次是对CN和C₅H₄N的吸附,在某些偏压下电流有大幅度的下降,其值 关键词： 碳链 输运特性 密度泛函理论 非平衡格林函数     

Vibration spectroscopy of benzene adsorbed on Pt(111) and Ni(111)

High resolution electron energy loss spectroscopy has been applied to study the adsorption of benzene (C₆H₆ and C₆D₆) on Pt(111) and Ni(111) single crystal surfaces between 140 and 320 K. The vibrational spectra provide evidence that benzene is chemisorbed with its ring parallel to the surface, predominantly π bonded to the platinum and nickel surface respectively. A significant frequency increase of the CH-out-of-plane bending mode, largest in the case of platinum, is observed compared to the free molecule. On both metals two phases of benzene exist simultaneously, characterized by a different frequency shift. The shifts are explained by electronic interaction between the metal d-orbitals and molecules adsorbed in on top and threefold hollow sites respectively. The vibrational spectra of the multilayer condensed phase of benzene exhibit the infrared active modes of the gasphase molecule as expected.     

Classical trajectory calculations for state-resolved Penning ionisation reactions of polycyclic aromatic hydrocarbon C10H8 in collision with He*(23S)

ABSTRACT

The reaction dynamics of Penning ionisation of a polycyclic aromatic hydrocarbon (PAH), naphthalene C₁₀H₈, in collision with the metastable He*(2³S) atom is studied by classical trajectory calculations using an approximate interaction potential energy surface between He* and the molecule, which is constructed based on ab initio calculations for the isovalent Li?+?C₁₀H₈ system. The ionisation width (rate) around the molecular surface are obtained from overlap integrals of the He 1s orbital and the molecular orbital. The calculated collision energy dependences of partial Penning ionisation cross sections (CEDPICS) in the range 50–500?meV at 300?K have reproduced the experimental results semi-quantitatively. The opacity functions, which represent the reaction probability with respect to the impact parameter b, are discussed in connection with collision energy, interaction with He* and the exterior electron density of molecular orbitals. They indicate that the collisional ionisations of C₁₀H₈ can be classified into three types: π electron ionisations with negative collision energy dependences which are predominantly determined by attractive interaction with He*; σ orbitals ionisations of the hardcore type; σ orbital ionisations which reflect interaction potentials around CH bonds. The critical impact parameters b_c become larger with increasing collision energy due to the centrifugal barrier.     

Structural impact on the methano bridge in norbornadiene, norbornene and norbornane

An electronic structural study of the ground electronic states for the chemically similar bicyclic norbornadiene (NBD, C₇H₈, X¹A₁), norbornene (NBN, C₇H₁₀, X¹A′) and norbornane (NBA, C₇H₁₂, X¹A₁) molecules is provided quantum mechanically. Initially, the unique orbital imaging capability of electron momentum spectroscopy is used to validate which of the quantum mechanical models available to us for these calculations best represents these species. Thereafter, individual molecular point group symmetry is incorporated in the calculations with energy minimization in the search for equilibrium geometries of the species using MP2/TZVP and B3LYP/TZVP models. The optimized geometries compare favourably with available crystallographic results and also build confidence in cases where the crystallographic results are ambiguous. The present study aims to reveal the particular subtle structural deviation of the species, which results in significant molecular property differences among these organic compounds. This work intends to probe bonding information of the species and the impact, on the seven member carbon skeleton, as the CC double bonds of NBD are progressively saturated by hydrogen atoms to give NBN and NBA. Significant changes observed through the present work include: (i) the seven member carbon skeleton tends to relax the strain whenever possible and (ii) the ethano ring experiences greater structural changes than the methano bridge. The methano bridge (C₍₁₎-C₍₇₎-C₍₄₎) of the less symmetric NBN molecule (C_s) tilts to the single C-C bond side of the ethano ring of the molecule (rather than the CC side), producing a dihedral angle of 8.7° between plane H-C₍₁₎-C₍₄₎ (the yz-plane) and plane C₍₁₎-C₍₇₎-C₍₄₎. Our work suggests that it is this unique dihedral angle in NBN which causes the molecules exo-reactivity and is also responsible for the extra activity of its CC bond.     

The adsorption of toluene on V-Sb oxides. Theoretical aspects

Toluene adsorption reactions on the (1 1 0) surface of VSbO₄ have been analyzed following the changes in the electronic structure of the hydrocarbon molecule and metal cation sites of the oxide using the Just Another Extended Hückel Molecular Orbital Program (JAEHMOP) code. The bonding character of these interactions has also been studied in the same theoretical framework. The calculations indicate that the exothermic hydrocarbon parallel interaction on Sb-V sites results in the weakening of one of the C-H bonds of the methyl fragment. This leads to a H-abstraction that involves the participation of a Sb-cation. Both methyl and phenyl fragments decrease their electronic population and so does the V-cation site. Most of these electrons are transferred to other V atoms in the bulk solid. As a result the LUMO of the toluene-oxide system fully populates. The analysis reveals that methyl-Sb bonding interactions mainly involve C_2px and H_1s orbitals with Sb_5s orbital, while non-bonding phenyl-V interactions involve C_2px orbitals with V_3dx²−y² orbital. This last interaction facilitates the desorption of the benzyl species after H-abstraction.     

Auger spectra of CO,C2H4, C2N2 and C6H6 adsorbed on Pt(111)

Electron excited carbon KVV Auger spectra of CO, C₂H₄, C₂N₂ and C₆H₆ adsorbed on Pt(111) are compared. By estimating the effective Coulomb interaction between the final-state holes it is possible to associate some features with transitions observed in free molecule spectra, but others must involve at least one electron with energy within the conduction band of the metal. Such “cross-transitions” are associated with strong 2π* character of filled states in the presence of a core hole in molecules such as CO.     

High-pressure hydrogenated fullerenes: Optical spectra and stability of C<Subscript>60</Subscript>H<Subscript>36</Subscript> at high pressure

The optical Raman and photoluminescence (PL) spectra of the high-pressure hydrogenated fullerene C₆₀ are studied at normal conditions and at high pressure. The Raman spectrum of the most stable hydrofullerene C₆₀H₃₆ contains a large number of peaks related to various isomers of this molecule. Comparison of the experimental data with the results of calculations shows that the most abundant isomers have the symmetries S₆, T, and D_3d. The Raman spectrum of deuterofullerene C₆₀H₃₆ is similar to that of C₆₀H₃₆, but the frequencies of the C-H stretching and bending modes are shifted due to the isotopic effect. The PL spectrum of hydrofullerene C₆₀H₃₆ is shifted to higher energies by approximately 1 eV with respect to that of pristine C₆₀. The effect of hydrostatic pressure on the Raman and PL spectra of C₆₀H₃₆ has been investigated up to 12 GPa. The pressure dependence of the phonon frequencies exhibits peculiarities at approximately 0.6 and 6 GPa. The changes observed at approximately 0.6 GPa are probably related to a phase transition from the initial orientationally disordered body-centered cubic structure to an orientationally ordered structure. The peculiarity at approximately 6 GPa may be related to a pressure-driven enhancement of the C-H interaction between the hydrogen and carbon atoms belonging to neighboring molecular cages. The pressure-induced shift of the photoluminescence spectrum of C₆₀H₃₆ is very small up to 6 GPa, and a negative pressure shift was observed at higher pressure. All the observed pressure effects are reversible with pressure.     

Assessment of the nature of interactions of cations with cycloheptatriene derivatives using change in the aromaticity: Comparison with electron density and NBO results

ABSTRACT

Interactions of cycloheptatriene derivatives, C₇H₆X, (X?=?NH, PH, AsH, O, S, Se) with the cations H⁺, CH₃⁺, Cu⁺, Al⁺, Li⁺, Na⁺, and K⁺ are studied using B3LYP functional and 6-311++G(d,p) basis set. The calculated gas-phase cation affinities (CA) and cation basicities (CB) for all molecules decrease as H⁺ > CH₃⁺ > Cu⁺ > Al⁺ > Li⁺ > Na⁺ > K⁺. We used the induced aromaticity in the 7-membered ring of C₇H₆X upon interaction with the cations, M⁺, as a measure of C₇H₆X/M⁺ interaction. Nucleus-independent chemical shift (NICS) and harmonic oscillator model of aromaticity (HOMA) were used as two indices of aromaticity. The highest and lowest induced aromaticities were observed for interactions of H⁺ and K⁺, respectively. Also, the aromaticity induced by interaction with a cation in C₇H₆AsH and C₇H₆PH was larger than that in C₇H₆NH and C₇H₆O. Hence, the aromaticity was considered as a measure of covalency for the C₇H₆X/M⁺ interactions showing a rational dependence on both the molecule and cation. The nature of the interactions was also assessed using electron density, charge distribution analysis and NBO calculations. The results of the aromaticity indices, NICS and HOMA, were compared with the electron density and NBO results.     

Structural conformations and electronic interactions of the natural product,oroxylin: a vibrational spectroscopic study

The oroxylin, 5,7‐dihydroxy 6‐methoxy flavone is a potent natural product extracted from ‘Vitex peduncularis’. Density functional theory (DFT) at B3LYP/6‐311G(d,p) level has been used to compute energies of different conformers of oroxylin to find out their stability, the optimized geometry of the most stable conformer and its vibrational spectrum. The conformer ORLN‐1 with torsion angles 0, 180, 180 and 0 degrees, respectively, for H₁₃ O₁₂ C₆ C₅, H₁₄ O₁₀ C₄ C₅, H₁₃ O₁₂ C₆ C₅ and H₁₄ O₁₀ C₄ C₅ is found to be most stable. The optimized geometry reveals that the dihedral angle φ between phenyl ring B and the chrome part of the molecule in − 19.21° is due to the repulsive force due to steric interaction between the ortho‐hydrogen atom H₂₉ of the B ring and H₁₈ of the ring C (H₂₉·H₁₈ = 2.198 Å). A vibrational analysis based on the near‐infrared Fourier transform(NIR‐FT) Raman, Fourier transform‐infrared (FT‐IR) and the computed spectrum reveals that the methoxy group is influenced by the oxygen lone pair‐aryl p_z orbital by back donation. Hence the stretching and bending vibrational modes of the methoxy group possess the lowest wavenumber from the normal values of methyl group. The carbonyl stretching vibrations have been lowered due to conjugation and hydrogen bonding in the molecules. The intramolecular H‐bonding and nonbonded intramolecular interactions shift the band position of O₁₀ H₁₄ and O₁₂ H₁₃ stretching modes, which is justified by DFT results. Copyright © 2008 John Wiley & Sons, Ltd.     

Substituent effects on the 13C NMR chemical shifts of the imine carbon in N‐(4‐X–benzylidene)‐4‐(4‐Y–styryl) anilines

Long‐range electronic substituent effects were targeted using the substituent dependence of δ_C(C═N), and specific cross‐interactions were explored extendedly. A wide set of N‐(4‐X–benzylidene)‐4‐(4‐Y–styryl) anilines, p‐X–C₆H₄CH═NC₆H₄CH═CHC₆H₄–p‐Y (X = NMe₂, OMe, Me, H, Cl, F, CN, or NO₂; Y = NMe₂, OMe, Me, H, Cl, or CN) were prepared for this study, and their ¹³C NMR chemical shifts δ_C(C═N) of C═N bonds were measured. The results show that both the inductive and resonance effects of the substituents Y on the δ_C(C═N) of p‐X–C₆H₄CH═NC₆H₄CH═CHC₆H₄–p‐Y are less than those of the substituents Y in p‐X–C₆H₄CH═NC₆H₄–p‐Y. Moreover, the sensitivity of the electronic character of the C═N function to electron donation/electron withdrawal by the substituent X or Y attenuates as the length of the conjugated chain is elongated. It was confirmed that the substituent cross‐interaction is an important factor influencing δ_C(C═N), not only when both X and Y are varied but also when either X or Y is fixed. The long‐range transmission of the specific cross‐interaction effects on δ_C(C═N) decreases with increasing conjugated distance between X and Y. The results of this study suggest that there is a long‐range transmission of the substituent effects in p‐X–C₆H₄CH═NC₆H₄CH═CHC₆H₄–p‐Y. Copyright © 2012 John Wiley & Sons, Ltd.