Radial breathing modes of single-walled carbon nanotubes in resonance Raman spectra at high temperature and their chiral index assignment

Radial breathing modes (RBMs) in resonance Raman spectra from single-walled carbon nanotubes (SWCNTs) on a SiO₂/Si (0 0 1) substrate are studied between 25 and 720 °C. A change in the relative intensity of each RBM peak with temperature is observed, which originates from the temperature dependence of the resonance condition of nanotubes. For 25 °C, each RBM peak is reasonably assigned on the basis of data in the literature [J. Maultzsch, H. Telg, S. Reich, F. Hennrich, C. Thomsen, Phys. Rev. B 72 (2005) 205438]. By taking into account the temperature-dependent behavior of the relative intensity of the RBM peaks, each RBM peak is successfully assigned even for 720 °C. It is found that most of the observed RBM peaks for a laser excitation energy of E_exc = 1.96 eV are from chiral SWCNTs. These results make it possible to discuss further details of the chirality-dependent growth behavior observed for in situ Raman spectroscopy.     

Scanning tunneling microscopy observation of initial growth of Sn and Ge1−xSnx layers on Ge(0 0 1) substrates

We have investigated the initial growth of Sn and Ge_1−xSn_x layers on Ge(0 0 1) surface by using scanning tunneling microscopy. After the growth of a 0.035 ML-thick Sn layer at room temperature, Sn clusters lining vertically to a dimer row was observed. In the case of the 0.035-0.018 ML-thick Sn growth at 250 °C, the characteristic surface reconstruction with the step-edge undulation like a comb was observed. In the growth of a Ge_0.994Sn_0.006 layer at 250 °C, the multilayer polynuclear growth with a lot of two-dimensional small domain was observed. These surface reconstructions should be accounted for by the large compressive stress induced in the surface layer due to the incorporation of Sn atoms.     

A systematic study of 3NF effects in p + d break-up with BINA at 190 MeV

A systematic study of three-nucleon force (3NF) effects in break-up reactions has been carried out at KVI at several energies. In this article, the p + d → p + p + n reaction with a polarized-proton beam of 190?MeV will be discussed. The experiment was performed by exploiting a new detector called BINA. Some results for high-precision vector analyzing powers and differential cross sections are presented and compared with state-of-the-art Faddeev calculations with or without 3NF.     

Rapid sea-level change in the Late Guadalupian (Permian) on the Tethyan side of South China: litho- and biostratigraphy of the Chaotian section in Sichuan

The Capitanian (Late Guadalupian) Maokou Formation at Chaotian in northern Sichuan, South China, is composed mainly of shallow marine shelf carbonates deposited on the Tethyan side of South China. By detailed field mapping and scientific drilling, we newly found out unique fossil assemblages and a sharp lithologic change in the upper part of the Maokou Formation. The main part of the Maokou Formation (over 130 m thick) is composed of algal packstone with Wordian-Capitanian large-tested fusulines, rugose corals and other sessile benthos, whereas the Uppermost Member (13 m thick) is composed of black limy mudstone/chert with Capitanian offshore biota (ammonoids, radiolarians, and conodonts). The topmost Capitanian conodont zones are missing; however, the Maokou Formation is disconformably overlain by 260+/-4 Ma volcanic ash (Wangpo bed) and the Early Lopingian Wujiaping Formation with plant-bearing coaly mudstone and shallow marine carbonates (packstone). The newly identified facies change indicates that northern Sichuan has experienced rapid sea-level changes in the late Guadalupian, i.e., first a transgression in the mid-Capitanian and then a regression across the Guadalupian-Lopingian boundary. As the end-Guadalupian is characterized by a global regression, such a volatile sea-level fluctuation, in particular the sea-level rise, is unique to the Tethyan side of South China. The newly recognized relatively deep-water late Guadalupian sequence adds new paleo-environmental information and further provides a paleotectonic interpretation of the low-latitude eastern Tethyan margin immediately before the end-Guadalupian mass extinction.     

Form factors and correlation functions of an interacting spinless fermion model

Introducing the fermionic R-operator and solutions of the inverse scattering problem for local fermion operators, we derive a multiple integral representation for zero-temperature correlation functions of a one-dimensional interacting spinless fermion model. Correlation functions particularly considered are the one-particle Green's function and the density–density correlation function both for any interaction strength and for arbitrary particle densities. In particular for the free fermion model, our formulae reproduce the known exact results. Form factors of local fermion operators are also calculated for a finite system.     

Possible mechanism of charge stripe formation based on the ring exchange interaction

Using the numerical diagonalization of the finite-cluster t–J model, we investigate the mechanism of the charge stripes based on the ring exchange interaction. We calculate the many-hole correlation functions related with the two-types of charge stripes; the vertical and diagonal types of the charge stripe. As a result, we present a phase diagram including the two stripe phases and a phase separation phase.     

Coumarin synthesis on π-acidic surfaces

Catalysis with anion–π interactions is emerging as an important topic in supramolecular chemistry. Among the reactions explored so far on π-acidic surfaces, coumarin synthesis stands out as a cascade process with several coupled anionic transition states. Increasing π-acidity has been shown in a different context to increase transition-state stabilisation and thus catalytic activity. In this report, we explore the possible use of macrocycles to accelerate coumarin synthesis between two π-acidic surfaces. To our disappointment, we found that compared to monomeric π-acids, coumarin synthesis within divalent macrocycles is clearly slower. Hindered access to an overly confined active site within the macrocycles could possibly account for this loss in activity, but several other explanations are certainly possible. However, operational coumarin synthesis on monomeric π-acidic surfaces is shown to tolerate structural modifications. Best results are obtained with structures that aim for proximity without obstructing transition-state stabilisation on the π-acidic surface.     

Big,Strong, Neutral,Twisted, and Chiral π Acids

General synthetic access to expanded π‐acidic surfaces of variable size, topology, chirality, and π acidity is reported. The availability of π surfaces with these characteristics is essential to develop the functional relevance of anion–π interactions with regard to molecular recognition, translocation, and transformation. The problem is that, with expanded π surfaces, the impact of electron‐withdrawing substituents decreases and the high π acidity needed for strong anion–π interactions can be more difficult to obtain. To overcome this problem, it is herein proposed to build large surfaces from smaller fragments and connect these fragments with bridges that are composed only of single atoms. Two central surfaces for powerful anion–π interactions, namely, perfluoroarenes and naphthalenediimides (NDIs), were selected as fragments and coupled with through sulfide bridges. Their oxidation to sulfoxides and sulfones, as well as fluorine substitution in the peripheral rings, provides access to the full chemical space of relevant π acidities. According to cyclic voltammetry, LUMO levels range from ?3.96 to ?4.72 eV. With sulfoxide bridges, stereogenic centers are introduced to further enrich the intrinsic planar chirality of the expanded surfaces. The stereoisomers were separated by chiral HPLC and characterized by X‐ray crystallography. Their topologies range from chairs to π boats, and the latter are reminiscent of the cation–π boxes in operational neuronal receptors. With pentafluorophenyl acceptors, the π acidity of NDIs with two sulfoxide groups in the core reaches ?4.45 eV, whereas two sulfone moieties give a value of ?4.72 eV, which is as low as with four ethyl sulfone groups, that is, a π superacid near the limit of existence. Beyond anion–π interactions, these conceptually innovative π‐acidic surfaces are also of interest as electron transporters in conductive materials.     

Near‐Infrared Light‐Driven Hydrogen Evolution from Water Using a Polypyridyl Triruthenium Photosensitizer

In order to realize artificial photosynthetic devices for splitting water to H₂ and O₂ (2 H₂O+hν→2 H₂+O₂), it is desirable to use a wider wavelength range of light that extends to a lower energy region of the solar spectrum. Here we report a triruthenium photosensitizer [Ru₃(dmbpy)₆(μ‐HAT)]⁶⁺ (dmbpy=4,4′‐dimethyl‐2,2′‐bipyridine, HAT=1,4,5,8,9,12‐hexaazatriphenylene), which absorbs near‐infrared light up to 800 nm based on its metal‐to‐ligand charge transfer (¹MLCT) transition. Importantly, [Ru₃(dmbpy)₆(μ‐HAT)]⁶⁺ is found to be the first example of a photosensitizer which can drive H₂ evolution under the illumination of near‐infrared light above 700 nm. The electrochemical and photochemical studies reveal that the reductive quenching within the ion‐pair adducts of [Ru₃(dmbpy)₆(μ‐HAT)]⁶⁺ and ascorbate anions affords a singly reduced form of [Ru₃(dmbpy)₆(μ‐HAT)]⁶⁺, which is used as a reducing equivalent in the subsequent water reduction process.