Structural model of silica nanowire assembled from a highly stable (SiO2)8 unit

The ground-state structures of silica clusters (SiO2)n for n = 1-8 were studied by performing calculations at the B3LYP/6-311+G(d) level of density functional theory. The results indicate that the growth mode of a silica nanowire based on small silica clusters may change at different wire lengths. A linear chain might be assembled from the smallest clusters of rhombic two-membered ring (2MR) with n < or = 5, while the growth motif changes at n = 6 into a more compact form composed of three-membered-rings (3MRs). The 3MR-containing structures become energetically favorable configurations for even longer silica clusters. In particular, the closed molecular ring consisting of 3MRs at n = 8 (i.e., (SiO2)8) with a high symmetry shows extreme energetic stability and relatively high chemical reactivity and thus is considered to be an important building block to assemble into silica nanowires. The relative stability of so-assembled silica nanowires were evaluated and compared with the models of silica nanowires in the literature.     

Density functional theory study of geometrical structures and electronic properties of silica nanowires

Silica nanowires are expected to possess structural diversity like bulk silica. We modeled three silica nanowires based on the side-shared two-membered rings, spiro-united two-membered rings, and three-membered rings, respectively. By performing density functional theory calculations, we studied their geometrical structures and electronic properties with and without the presence of external electric field. It is found that the stability of silica nanowires increases with length and diameter. As indicated by calculated large HOMO-LUMO gaps, silica nanowires are expected to be good insulating materials. The energy gaps, however, gradually decrease with applied electronic field and finally close, resulting in the breakdown of the insulating nanowires. Moreover, it is shown that the breakdown threshold remarkably increases with the nanowire diameter. These significant findings from the present calculations for the simplest silica nanowires will provide relevant insight into the structures and properties of much more complicated real silica nanowires.     

InAs管状团簇及单壁InAs纳米管的结构、稳定性和电子性质

采用密度泛函理论研究了InnAsn (n≤90)管状团簇以及单壁InAs纳米管的几何结构、稳定性和电子性质. 小团簇InnAsn (n=1-3)基态结构和电子性质的计算结果与已有报道相一致. 当n≥4时优化得到了一族稳定的管状团簇, 其结构基元(In原子与As原子交替排列的四元环和六元环结构)满足共同的衍化通式. 团簇的平均结合能表明横截面为八个原子的管状团簇稳定性最好. 管状团簇前线轨道随尺寸的变化规律有效地解释了一维稳定管状团簇的生长原因, 同时也说明了实验上之所以能合成InAs纳米管的微观机理. 此外, 研究结果表明通过管状团簇的有效组装可得到宽带隙的InAs半导体单壁纳米管.     

Theoretical study on the structure and stability of some unusual boron-nitrogen helices

Ab initio self-consistent field molecular orbital and density functional theory calculations have been performed on a series of helical structures comprised of boron-nitrogen analogues of extended helicenes, with helically arranged N fused benzene rings, and alternating N benzene units fused to N - 1 cyclobutadiene rings as reference structures. The electronic structure and stability of boron-nitrogen analogues of angular [N]helicenes, [N]phenylenes (N = 5, 6, 7, 12), and [N]methylenylnaphthalenes (N = 6) were investigated at the HF/6-31G(d) and the B3LYP/6-31G(d) levels of theory. The presence of an even number N of rings in the boron-nitrogen [N]helicenes leads to the possibility of angular isomers. Electron density contours were calculated in order to interpret the existing bonding patterns. These structures may provide supramolecular building blocks and macromolecular "springs" with unusual electronic properties.     

Structural and electronic properties of borazine cyclacenes

The structural and electronic properties of borazine cyclacenes (BNn) have been investigated by performing semiempirical molecular orbital self-consistent field calculations at the level of AM1 method within the RHF formulation. It has been found that as the number of borazine rings increases in the arenoid belt the structures become more exothermic.     

Chromium aromatic hydrocarbon sandwich molecules and the eighteen-electron rule

Ab initio density functional theory (DFT) calculations are reported for the chromium sandwich structure CrnR2, where n = 7 and R is the aromatic hydrocarbon hexabenzocoronene (C42H18). This system is remarkable in that the structure of the chromium sites strongly resemble those in chromium bis-benzene Cr1(C6H6)2, as judged by geometry and charge density properties. The electron localization function of the sandwich shows a hexagonally arrayed set of V(C, Cr, C) valence basins about each chromium atom with modification due to local site symmetry. This system satisfies an extension of the 18-electron rule to components of a conjugated molecular system. This idea is explored further by examining the electronic and geometric properties of the series CrnR2, where n and R are given by n = 1, benzene C6H6 as reference; n = 2, biphenyl (C6H5)2; n = 3, triphenylene C18H12; n = 3, coronene C24H18; and n = 4, dibenzopyrene C24H14. On the basis of electron counting and ring isolation, all the sandwich structures in this series could satisfy the extension of the 18-electron rule, with the exception of coronene, which was deliberately included. The DFT calculations predict spin-paired ground states for some but not all of the sandwich structures, implying that the Cr-ring interactions at work require understanding at a deeper level. Thus, while sandwiches with n = 1, n = 2, n = 4 and n = 7 have spin paired singlet ground states and appear to satisfy the rule, those with n = 3 (triphenylene, coronene) have antiferromagnetic singlet ground states and do not. This is attributed to nonuniformity in the electronic charge density of the rings of the isolated hydrocarbons and to a reduction of symmetry from D3h to C2v with a concomitant spin-charge density change in the sandwiches.     

New type of bonding formed from an overlap between pi aromatic and pi C=O molecular orbitals stabilizes the coexistence in one molecule of the ionic and neutral meso-ionic forms of imidazopyridine

New bis(imidazo)pyridine dye has been synthesized and tested as a potential photoinitaitor for free-radical polymerization induced with the visible emission of an argon ion laser. The X-ray analysis based on data collected at 170 and 130 K, as well as density functional theory (DFT) calculations, revealed the presence of two different forms of imidazopyridine rings within the same molecule. These two forms of the same moiety had not only different geometries but different electronic structures as well. One of the imidazopyridine rings was in the ionic form, while the other was in the meso-ionic form. DFT calculations provided an explanation for such an observed phenomena. The averaging of ionic and meso-ionic forms of imidazopyridine rings within the same molecule is hindered because of an attractive interaction between them. Analysis of electronic density revealed that, indeed, a new type of bonding is formed as the result of an overlap between pi aromatic and pi C=O molecular orbitals. This bonding, like the hydrogen bond, is primarily of electrostatic character, and its energy was estimated at 3.5 kcal/mol.     

Polymorphic porous supramolecular networks mediated by halogen bonds on Ag(111)

Intermolecular structures of porous two-dimensional supramolecular networks are studied using scanning tunnelling microscopy combined with density functional theory calculations. The local configurations of halogen bonds in polymorphic porous supramolecular networks are directly visualized in support of previous bulk crystal studies.     

Toward uniform nanotubular compounds: synthetic approach and ab initio calculations

We propose to synthesize a new class of single-walled nanotubular compounds (SWNCs) and investigate the interplay between their structural and electronic properties using ab initio density functional calculations. SWNCs are composed of cyclacenes of variable diameter interconnected by various linker compounds. Cyclacenes map directly onto and can be viewed as the shortest segments of (n,0) zigzag carbon nanotubes. We focus on cyclacenes with n=6-12 fused benzene rings interconnected by biphenyl, tetrazine, or acetylene linkers. Depending upon the nature and the orientation of the linkers, we find it possible to change the systems from narrow-gap to wide-gap semiconductors, and to modulate the band dispersion, suggesting the possibility of band gap engineering.     

σ Aromaticity Dominates in the Unsaturated Three‐Membered Ring of Cyclopropametallapentalenes from Groups 7–9: A DFT Study

Aromaticity, an old but still fantastic topic, has long attracted considerable interest of chemists. Generally, π aromaticity is described by π‐electron delocalization in closed circuits of unsaturated compounds whereas σ‐electron delocalization in saturated rings leads to σ aromaticity. Interestingly, our recent study shows that σ aromaticity can be dominating in an unsaturated three‐membered ring (3MR) of cyclopropaosmapentalene. An interesting question is raised: Can the σ aromaticity, which is dominant in the unsaturated 3MR, be extended to other cyclopropametallapentalenes? If so, how could the metal centers, ligands, and substituents affect the σ aromaticity? Here, we report a thorough theoretical study on these issues. The nucleus‐independent chemical shift calculations and the anisotropy of the current‐induced density plots reveal the dominant σ aromaticity in these unsaturated 3MRs. In addition, our calculations show that substituents on the 3MRs have significant effects on the σ aromaticity, whereas the ligand effect is particularly small.     

DFT Study on the Electronic and Structural Properties of ReO5-/0 Clusters

The electronic and structural properties of ReO5 and ReO5 clusters are investigated using density functional theory (DFT) calculations. The lowest energy structures for both the anionic and neutral clusters are determined, and the corresponding photoelectron spectrum is simulated. Our results show that ReO5 can be described as an unusual peroxo molecule, Re(O)3(η2-O2) , while ReO5 is found to be exhibiting the O2 o radical character. Molecular orbital analyses and spin density analyses are performed to elucidate the chemical bonding and the electronic and structural properties in these two rhenium oxide clusters.     

Structure determination and characterization of two rare-earth molybdenum borate compounds: LnMoBO(6) (Ln = La, Ce)

The structural, optical, and electronic properties of two rare-earth molybdenum borate compounds, LnMoBO(6) (Ln = La, Ce), have been investigated by means of single-crystal X-ray diffraction, elemental analyses, and spectral measurements, as well as calculations of energy band structures, density of states, and optical response functions by the density functional method. The title compounds, which crystallize in monoclinic space group P2(1)/c, possess a similar network of interconnected [Ce(2)(MoO(4))(2)](2+) chains and [BO(2)](-) wavy chains. Novel 1D molybdenum oxide chains are contained in their three-dimensional (3D) networks. The calculated results of crystal energy band structure by the density functional theory (DFT) method show that the solid-state compound LaMoBO(6) is a semiconductor with indirect band gaps.     

Exploring the Molecular Structure of Imidazolium–Silica‐Based Nanoparticle Networks by Combining Solid‐State NMR Spectroscopy and First‐Principles Calculations

A DFT‐based molecular model for imidazolium–silica‐based nanoparticle networks (INNs) is presented. The INNs were synthesized and characterized by using small‐angle X‐ray scattering (SAXS), NMR spectroscopy, and theoretical ab initio calculations. ¹¹B and ³¹P HETCOR CP MAS experiments were recorded. Calculated ¹⁹F NMR spectroscopy results, combined with the calculated anion–imidazolium (IM) distances, predicted the IM chain density in the INN, which was also confirmed from thermogravimetric analysis/mass spectrometry results. The presence of water molecules trapped between the nanoparticles is also suggested. First considerations on possible π–π stacking between the IM rings are presented. The predicted electronic properties confirm the photoluminescence emissions in the correct spectral domain.     

Dimensional dependence of electronic structure of fullerene polymers

Fullerene polymers made of C(60) are systematically investigated by means of a first-principles pseudopotential approach within the local density approximation of the density functional theory. We assume 10 different structures of fullerene polymers. The first three are C(60) polymer networks cross-linked by [2+2] cycloadditional four-membered rings, and the other seven are composed of peanut-shaped fused C(60) polymer chains cross-linked by either seven-membered rings or eight-membered rings. Owing to the overlap of wave functions as well as the hybrid networks of sp(2)-like (3-fold coordinated) and sp(3)-like (4-fold coordinated) carbon atoms, the electronic structure is considerably different from each other. We find that the resulting electronic structure is either semiconductor or semimetal depending on the spatial dimensionality of materials.     

Synthesis of a Porous [14]Annulene Graphene Nanoribbon and a Porous [30]Annulene Graphene Nanosheet on Metal Surfaces

The electrical and mechanical properties of graphene-based materials can be tuned by the introduction of nanopores, which are sensitively related to the size, morphology, density, and location of nanopores. The synthesis of low-dimensional graphene nanostructures containing well-defined nonplanar nanopores has been challenging due to the intrinsic steric hindrance. Herein, we report the selective synthesis of one-dimensional (1D) graphene nanoribbons (GNRs) containing periodic nonplanar [14]annulene pores on Ag(111) and two-dimensional (2D) porous graphene nanosheet containing periodic nonplanar [30]annulene pores on Au(111), starting from a same precursor. The formation of distinct products on the two substrates originates from the different thermodynamics and kinetics of coupling reactions. The reaction mechanisms were confirmed by a series of control experiments, and the appropriate thermodynamic and kinetic parameters for optimizing the reaction pathways were proposed. In addition, the combined scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations revealed the electronic structures of porous graphene structures, demonstrating the impact of nonplanar pores on the π-conjugation of molecules.     

Substitution Effect in NICS Values in Tropylium Ion Derivatives: An Ab Initio Study

Hartree–Fock (HF) and hybrid density functional theory (B3LYP) calculations were performed on tropylium ion and 19 of its mono- and diheteroatomic derivatives. The aromaticity in this class of compounds is evaluated based on the nucleus independent chemical shift (NICS) values. The NICS values are calculated at the center of the rings NICS (0) and at 1Å above the molecular plane NICS (1). The geometry optimization and NICS calculations were carried out at the HF/6–311+G?? and at the B3LYP/6–311+G (2d, p) density functional level, respectively. These calculations in the effects of heteroatoms such as N, B, P, and Si are considered on aromaticity, molecular properties, NICS values, and structural parameters.     

Plane-wave calculations applied to conjugated polymers

Density functional calculations using pseudopotentials and a plane-wave basis set are applied to study the geometry and the electronic structure of conjugated polymers consisting of heterocyclic aromatic rings. This article focuses on the computational methods. The influence of the pseudopotentials on the structural and electronic properties is studied. The rates of convergence of these properties with respect to the basis set size and the density of sampling points for the Brillouin zone integration are considered. The effects of using different exchange–correlation potentials (local density or generalized gradient approximations) are examined. It is shown that smooth norm-conserving pseudopotentials used for calculations on conjugated polymers lead to converged results with a moderately sized basis set. Received: 20 August 1999 / Accepted: 23 November 1999 / Published online: 19 April 2000     

A family of stable silica fullerenes with fully coordinated structures

Theoretical electronic structure techniques have become an indispensable and powerful tool for predicting molecular properties and designing new materials. The discovery of C(60) opened a challenging field in nanoscale materials science, and since then people have been looking for its inorganic analogues. On the basis of the B3LYP/6-31G(d) calculations, here we provide theoretical evidence for a family of stable silica fullerenes with fully coordinated structures, which exhibit highly structural and energetic stabilities, very large energy gaps, and extremely good resistibilities to breakdown of the insulating capability in an applied electric field. Our calculations indicate that the discrete silica fullerenes are a possible polymorph of silica and can be synthesized under some conditions. They are expected to find novel applications in silica-based molecular devices. The present results may provide an aid in the experimental design for controllably producing desired silica clusters.     

Guanine crystals: a first principles study

We report first principles density functional theory studies on the basic ground state characteristics, dynamic properties, and the electronic structure of guanine crystals. The effect of water molecules within the crystal is studied in detail, and we discuss their influence on the structural, vibrational, and electronic properties. The geometries calculated for various crystal structures are compared with gas-phase calculations and available experimental data. Phonon frequencies and eigenvectors are predicted for intermolecular and intramolecular lattice vibrations. Vibrational and electronic density-of-states are presented and analyzed. The electronic band structure near the fundamental gap is calculated from the Kohn-Sham approach. We find that the former molecular HOMO states form a dispersive band in the pi-pi stacking direction upon condensation resulting in a large bandwidth of 0.83 eV. Consequences for the charge transport in layered van der Waals bonded organic molecular crystals are discussed.