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04 May 06:44

Local Spectroscopic Characterization of Spin and Layer Polarization in WSe$_2$. (arXiv:1505.00245v2 [cond-mat.mes-hall] UPDATED)

by Matthew Yankowitz, Devin McKenzie, Brian J. LeRoy

We report scanning tunneling microscopy (STM) and spectroscopy (STS) measurements of monolayer and bilayer WSe$_2$. We measure a band gap of 2.21 $\pm$ 0.08 eV in monolayer WSe$_2$, which is much larger than the energy of the photoluminescence peak indicating a large excitonic binding energy. We additionally observe significant electronic scattering arising from atomic-scale defects. Using Fourier transform STS (FT-STS), we map the energy versus momentum dispersion relations for monolayer and bilayer WSe$_2$. Further, by tracking allowed and forbidden scattering channels as a function of energy we infer the spin texture of both the conduction and valence bands. We observe a large spin-splitting of the valence band due to strong spin-orbit coupling, and additionally observe spin-valley-layer coupling in the conduction band of bilayer WSe$_2$.

30 Apr 19:26

[Special Issue Review] Transforming the optical landscape

by J. B. Pendry
Electromagnetism provides us with some of the most powerful tools in science, encompassing lasers, optical microscopes, magnetic resonance imaging scanners, radar, and a host of other techniques. To understand and develop the technology requires more than a set of formal equations. Scientists and engineers have to form a vivid picture that fires their imaginations and enables intuition to play a full role in the process of invention. It is to this end that transformation optics has been developed, exploiting Faraday’s picture of electric and magnetic fields as lines of force, which can be manipulated by the electrical permittivity and magnetic permeability of surrounding materials. Transformation optics says what has to be done to place the lines of force where we want them to be. Authors: J. B. Pendry, Yu Luo, Rongkuo Zhao
30 Apr 19:26

[Special Issue Review] Nanophotonics: Shrinking light-based technology

by A. Femius Koenderink
The study of light at the nanoscale has become a vibrant field of research, as researchers now master the flow of light at length scales far below the optical wavelength, largely surpassing the classical limits imposed by diffraction. Using metallic and dielectric nanostructures precisely sculpted into two-dimensional (2D) and 3D nanoarchitectures, light can be scattered, refracted, confined, filtered, and processed in fascinating new ways that are impossible to achieve with natural materials and in conventional geometries. This control over light at the nanoscale has not only unveiled a plethora of new phenomena but has also led to a variety of relevant applications, including new venues for integrated circuitry, optical computing, solar, and medical technologies, setting high expectations for many novel discoveries in the years to come. Authors: A. Femius Koenderink, Andrea Alù, Albert Polman
30 Apr 09:38

A Small Molecule Walks Along a Surface Between Porphyrin Fences That Are Assembled In Situ

by Sam Haq, Bareld Wit, Hongqian Sang, Andrea Floris, Yu Wang, Jianbo Wang, Lluïsa Pérez-García, Lev Kantorovitch, David B. Amabilino, Rasmita Raval

Abstract

An on-surface bimolecular system is described, comprising a simple divalent bis(imidazolyl) molecule that is shown to “walk” at room temperature via an inchworm mechanism along a specific pathway terminated at each end by oligomeric “fences” constructed on a monocrystalline copper surface. Scanning tunneling microscopy shows that the motion of the walker occurs along the [1equation image0] direction of the Cu surface with remarkably high selectivity and is effectively confined by the orthogonal construction of covalent porphyrin oligomers along the [001] surface direction, which serve as barriers. Density functional theory shows that the mobile molecule walks by attaching and detaching the nitrogen atoms in its imidazolyl “legs” to and from the protruding close-packed rows of the metal surface and that it can transit between two energetically equivalent extended and contracted conformations by overcoming a small energy barrier.

Thumbnail image of graphical abstract

Walk the line: A bis(imidazolyl) compound “walks” along an anisotropic monocrystalline copper surface in one preferred direction with remarkably high selectivity. The motion of the walker can be effectively confined by on-surface synthesis of porphyrin oligomer fences oriented orthogonal to the walking direction, which act as insurmountable barriers.

29 Apr 19:54

Topological valley transport at bilayer graphene domain walls

by Long Ju

Topological valley transport at bilayer graphene domain walls

Nature 520, 7549 (2015). doi:10.1038/nature14364

Authors: Long Ju, Zhiwen Shi, Nityan Nair, Yinchuan Lv, Chenhao Jin, Jairo Velasco, Claudia Ojeda-Aristizabal, Hans A. Bechtel, Michael C. Martin, Alex Zettl, James Analytis & Feng Wang

Electron valley, a degree of freedom that is analogous to spin, can lead to novel topological phases in bilayer graphene. A tunable bandgap can be induced in bilayer graphene by an external electric field, and such gapped bilayer graphene is predicted to be a topological insulating phase protected by no-valley mixing symmetry, featuring quantum valley Hall effects and chiral edge states. Observation of such chiral edge states, however, is challenging because inter-valley scattering is induced by atomic-scale defects at real bilayer graphene edges. Recent theoretical work has shown that domain walls between AB- and BA-stacked bilayer graphene can support protected chiral edge states of quantum valley Hall insulators. Here we report an experimental observation of ballistic (that is, with no scattering of electrons) conducting channels at bilayer graphene domain walls. We employ near-field infrared nanometre-scale microscopy (nanoscopy) to image in situ bilayer graphene layer-stacking domain walls on device substrates, and we fabricate dual-gated field effect transistors based on the domain walls. Unlike single-domain bilayer graphene, which shows gapped insulating behaviour under a vertical electrical field, bilayer graphene domain walls feature one-dimensional valley-polarized conducting channels with a ballistic length of about 400 nanometres at 4 kelvin. Such topologically protected one-dimensional chiral states at bilayer graphene domain walls open up opportunities for exploring unique topological phases and valley physics in graphene.

29 Apr 19:50

A circuit mechanism for differentiating positive and negative associations

by Praneeth Namburi

A circuit mechanism for differentiating positive and negative associations

Nature 520, 7549 (2015). doi:10.1038/nature14366

Authors: Praneeth Namburi, Anna Beyeler, Suzuko Yorozu, Gwendolyn G. Calhoon, Sarah A. Halbert, Romy Wichmann, Stephanie S. Holden, Kim L. Mertens, Melodi Anahtar, Ada C. Felix-Ortiz, Ian R. Wickersham, Jesse M. Gray & Kay M. Tye

The ability to differentiate stimuli predicting positive or negative outcomes is critical for survival, and perturbations of emotional processing underlie many psychiatric disease states. Synaptic plasticity in the basolateral amygdala complex (BLA) mediates the acquisition of associative memories, both positive and negative. Different populations of BLA neurons may encode fearful or rewarding associations, but the identifying features of these populations and the synaptic mechanisms of differentiating positive and negative emotional valence have remained unknown. Here we show that BLA neurons projecting to the nucleus accumbens (NAc projectors) or the centromedial amygdala (CeM projectors) undergo opposing synaptic changes following fear or reward conditioning. We find that photostimulation of NAc projectors supports positive reinforcement while photostimulation of CeM projectors mediates negative reinforcement. Photoinhibition of CeM projectors impairs fear conditioning and enhances reward conditioning. We characterize these functionally distinct neuronal populations by comparing their electrophysiological, morphological and genetic features. Overall, we provide a mechanistic explanation for the representation of positive and negative associations within the amygdala.

29 Apr 19:50

High-mobility three-atom-thick semiconducting films with wafer-scale homogeneity

by Kibum Kang

High-mobility three-atom-thick semiconducting films with wafer-scale homogeneity

Nature 520, 7549 (2015). doi:10.1038/nature14417

Authors: Kibum Kang, Saien Xie, Lujie Huang, Yimo Han, Pinshane Y. Huang, Kin Fai Mak, Cheol-Joo Kim, David Muller & Jiwoong Park

The large-scale growth of semiconducting thin films forms the basis of modern electronics and optoelectronics. A decrease in film thickness to the ultimate limit of the atomic, sub-nanometre length scale, a difficult limit for traditional semiconductors (such as Si and GaAs), would bring wide benefits for applications in ultrathin and flexible electronics, photovoltaics and display technology. For this, transition-metal dichalcogenides (TMDs), which can form stable three-atom-thick monolayers, provide ideal semiconducting materials with high electrical carrier mobility, and their large-scale growth on insulating substrates would enable the batch fabrication of atomically thin high-performance transistors and photodetectors on a technologically relevant scale without film transfer. In addition, their unique electronic band structures provide novel ways of enhancing the functionalities of such devices, including the large excitonic effect, bandgap modulation, indirect-to-direct bandgap transition, piezoelectricity and valleytronics. However, the large-scale growth of monolayer TMD films with spatial homogeneity and high electrical performance remains an unsolved challenge. Here we report the preparation of high-mobility 4-inch wafer-scale films of monolayer molybdenum disulphide (MoS2) and tungsten disulphide, grown directly on insulating SiO2 substrates, with excellent spatial homogeneity over the entire films. They are grown with a newly developed, metal–organic chemical vapour deposition technique, and show high electrical performance, including an electron mobility of 30 cm2 V−1 s−1 at room temperature and 114 cm2 V−1 s−1 at 90 K for MoS2, with little dependence on position or channel length. With the use of these films we successfully demonstrate the wafer-scale batch fabrication of high-performance monolayer MoS2 field-effect transistors with a 99% device yield and the multi-level fabrication of vertically stacked transistor devices for three-dimensional circuitry. Our work is a step towards the realization of atomically thin integrated circuitry.

29 Apr 17:52

Model for Oxygen Interstitial Injection from the Rutile TiO2(110) Surface into the Bulk

by Kristine M. Pangan-Okimoto, Prashun Gorai, Alice G. Hollister and Edmund G. Seebauer

TOC Graphic

The Journal of Physical Chemistry C
DOI: 10.1021/acs.jpcc.5b02009
29 Apr 17:46

Single-Molecule Imaging of Activated Nitrogen Adsorption on Individual Manganese Phthalocyanine

by Jia Lin Zhang, Zhunzhun Wang, Jian Qiang Zhong, Kai Di Yuan, Qian Shen, Lei Lei Xu, Tian Chao Niu, Cheng Ding Gu, Christopher A. Wright, Anton Tadich, Dongchen Qi, He Xing Li, Kai Wu, Guo Qin Xu, Zhenyu Li and Wei Chen

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Nano Letters
DOI: 10.1021/acs.nanolett.5b00290
27 Apr 22:35

Direct Synthesis of Vanadium Phthalocyanine and Its Electronic and Magnetic States in Monolayers and Multilayers on Ag(111)

by Keitaro Eguchi, Takeshi Nakagawa, Yasumasa Takagi and Toshihiko Yokoyama

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The Journal of Physical Chemistry C
DOI: 10.1021/jp512935v
27 Apr 17:22

Tunable Light–Matter Interaction and the Role of Hyperbolicity in Graphene–hBN System

by Anshuman Kumar, Tony Low, Kin Hung Fung, Phaedon Avouris and Nicholas X. Fang

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.5b01191
27 Apr 12:34

Benzene-Fused Azacorannulene Bearing an Internal Nitrogen Atom

by Shingo Ito, Yuki Tokimaru, Kyoko Nozaki

Abstract

A novel nitrogen-doped corannulene derivative, 8-tert-butyl-6b2-azapentabenzo[bc,ef,hi,kl,no]corannulene, was synthesized by 1,3-dipolar cycloaddition of a polycyclic aromatic azomethine ylide with a diarylethyne and subsequent palladium-catalyzed intramolecular cyclization. This molecule represents the first example of a corannulene derivative bearing an internal heteroatom, and exhibits unique structural and physical properties caused by the introduction of the nitrogen atom and extended π-conjugation, as compared to the parent corannulene.

Thumbnail image of graphical abstract

Bowled over: A novel benzene-fused azacorannulene (left) was synthesized by the 1,3-dipolar cycloaddition of a polycyclic aromatic azomethine ylide with a diarylethyne and subsequent palladium-catalyzed intramolecular cyclization. This molecule represents the first example of a heteroatom-doped corannulene derivative and in the solid state bowl-in-bowl columnar π-stacking is observed (right).

25 Apr 13:07

Scanning Tunneling Microscopy and Density Functional Theory Study on Zinc(II)-Phthalocyanine Tetrasulfonic Acid on Bilayer Epitaxial Graphene on Silicon Carbide(0001)

by Dylan Nicholls, Run R. Li, Benjamin Ware, Christopher Pansegrau, Deniz Çakir, Mark R. Hoffmann and Nuri Oncel

TOC Graphic

The Journal of Physical Chemistry C
DOI: 10.1021/acs.jpcc.5b00864
24 Apr 10:08

Deep and Shallow TiO2 Gap States on Cleaved Anatase Single Crystal (101) Surfaces, Nanocrystalline Anatase Films, and ALD Titania Ante and Post Annealing

by Philip Reckers, Mariel Dimamay, Joachim Klett, Sara Trost, Kirill Zilberberg, Thomas Riedl, Bruce A. Parkinson, Joachim Brötz, Wolfram Jaegermann and Thomas Mayer

TOC Graphic

The Journal of Physical Chemistry C
DOI: 10.1021/acs.jpcc.5b01264
24 Apr 10:01

Hexagonal Boron Nitride Cover on Pt(111): A New Route to Tune Molecule–Metal Interaction and Metal-Catalyzed Reactions

by Yanhong Zhang, Xuefei Weng, Huan Li, Haobo Li, Mingming Wei, Jianping Xiao, Zhi Liu, Mingshu Chen, Qiang Fu and Xinhe Bao

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Nano Letters
DOI: 10.1021/acs.nanolett.5b01205
23 Apr 07:26

Unusual Deprotonated Alkynyl Hydrogen Bonding in Metal-Supported Hydrocarbon Assembly

by Yi-Qi Zhang, Jonas Björk, Peter Weber, Raphael Hellwig, Katharina Diller, Anthoula C. Papageorgiou, Seung Cheol Oh, Sybille Fischer, Francesco Allegretti, Svetlana Klyatskaya, Mario Ruben, Johannes V. Barth and Florian Klappenberger

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The Journal of Physical Chemistry C
DOI: 10.1021/acs.jpcc.5b02955
23 Apr 07:24

Controlled complete suppression of single-atom inelastic spin and orbital cotunnelling. (arXiv:1504.05882v2 [cond-mat.mes-hall] UPDATED)

by B. Bryant, R. Toskovic, A. Ferrón, J. L. Lado, A. Spinelli, J. Fernández-Rossier, A. F. Otte

The inelastic portion of the tunnel current through an individual magnetic atom grants unique access to read out and change the atom's spin state, but it also provides a path for spontaneous relaxation and decoherence. Controlled closure of the inelastic channel would allow for the latter to be switched off at will, paving the way to coherent spin manipulation in single atoms. Here we demonstrate complete closure of the inelastic channels for both spin and orbital transitions due to a controlled geometric modification of the atom's environment, using scanning tunnelling microscopy (STM). The observed suppression of the excitation signal, which occurs for Co atoms assembled into chain on a Cu$_2$N substrate, indicates a structural transition affecting the d$_z$$^2$ orbital, effectively cutting off the STM tip from the spin-flip cotunnelling path.

22 Apr 22:42

Phonon counting and intensity interferometry of a nanomechanical resonator

by Justin D. Cohen

Phonon counting and intensity interferometry of a nanomechanical resonator

Nature 520, 7548 (2015). doi:10.1038/nature14349

Authors: Justin D. Cohen, Seán M. Meenehan, Gregory S. MacCabe, Simon Gröblacher, Amir H. Safavi-Naeini, Francesco Marsili, Matthew D. Shaw & Oskar Painter

In optics, the ability to measure individual quanta of light (photons) enables a great many applications, ranging from dynamic imaging within living organisms to secure quantum communication. Pioneering photon counting experiments, such as the intensity interferometry performed by Hanbury Brown and Twiss to measure the angular width of visible stars, have played a critical role in our understanding of the full quantum nature of light. As with matter at the atomic scale, the laws of quantum mechanics also govern the properties of macroscopic mechanical objects, providing fundamental quantum limits to the sensitivity of mechanical sensors and transducers. Current research in cavity optomechanics seeks to use light to explore the quantum properties of mechanical systems ranging in size from kilogram-mass mirrors to nanoscale membranes, as well as to develop technologies for precision sensing and quantum information processing. Here we use an optical probe and single-photon detection to study the acoustic emission and absorption processes in a silicon nanomechanical resonator, and perform a measurement similar to that used by Hanbury Brown and Twiss to measure correlations in the emitted phonons as the resonator undergoes a parametric instability formally equivalent to that of a laser. Owing to the cavity-enhanced coupling of light with mechanical motion, this effective phonon counting technique has a noise equivalent phonon sensitivity of 0.89 ± 0.05. With straightforward improvements to this method, a variety of quantum state engineering tasks using mesoscopic mechanical resonators would be enabled, including the generation and heralding of single-phonon Fock states and the quantum entanglement of remote mechanical elements.

22 Apr 18:54

Cycloaddition of Metal Porphines on Metal-Supported Graphene: A Computational Study

by M. Lattelais and M.-L. Bocquet

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The Journal of Physical Chemistry C
DOI: 10.1021/jp512247n
22 Apr 18:49

Cobalt–Salen Complexes as Catalyst Precursors for Electrocatalytic Water Oxidation at Low Overpotential

by Haiyan Chen, Zijun Sun, Xiang Liu, Ali Han and Pingwu Du

TOC Graphic

The Journal of Physical Chemistry C
DOI: 10.1021/jp511584z
22 Apr 18:45

All Chemical Vapor Deposition Growth of MoS2:h-BN Vertical van der Waals Heterostructures

by Shanshan Wang, Xiaochen Wang and Jamie H. Warner

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ACS Nano
DOI: 10.1021/acsnano.5b00655
22 Apr 18:34

C_{60}

by J. Ledieu, É. Gaudry, M.-C. de Weerd, P. Gille, R. D. Diehl, and V. Fournée

Author(s): J. Ledieu, É. Gaudry, M.-C. de Weerd, P. Gille, R. D. Diehl, and V. Fournée

We report the formation of an ordered C60 monolayer on the Al9Co2(001) surface using scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), x-ray and ultraviolet photoelectron spectroscopy (XPS/UPS), and ab initio calculations. Dosing fullerenes at 300 K results in a disordered...


[Phys. Rev. B 91, 155418] Published Fri Apr 17, 2015

22 Apr 16:15

Transfering spin into an extended π orbital of a large molecule

by Taner Esat, Thorsten Deilmann, Benedikt Lechtenberg, Christian Wagner, Peter Krüger, Ruslan Temirov, Frithjof B. Anders, Michael Rohlfing, and F. Stefan Tautz

Author(s): Taner Esat, Thorsten Deilmann, Benedikt Lechtenberg, Christian Wagner, Peter Krüger, Ruslan Temirov, Frithjof B. Anders, Michael Rohlfing, and F. Stefan Tautz

By means of low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS), we have investigated the adsorption of single Au atoms on a PTCDA monolayer physisorbed on the Au(111) surface. A chemical reaction between the Au atom and the PTCDA molecule leads to the formation of a radical t...


[Phys. Rev. B 91, 144415] Published Mon Apr 20, 2015

22 Apr 16:12

Influence of atomic tip structure on the intensity of inelastic tunneling spectroscopy data analyzed by combined scanning tunneling spectroscopy, force microscopy and density functional theory. (arXiv:1504.04790v2 [cond-mat.mes-hall] UPDATED)

by Norio Okabayashi, Alexander Gustafsson, Angelo Peronio, Magnus Paulsson, Toyoko Arai, Franz J. Giessibl

Achieving a high intensity in inelastic scanning tunneling spectroscopy (IETS) is important for precise measurements. The intensity of the IETS signal can vary up to a factor three for various tips without an apparent reason accessible by scanning tunneling microscopy (STM) alone. Here, we show that combining STM and IETS with atomic force microscopy enables carbon monoxide front atom identification, revealing that high IETS intensities for CO/Cu(111) are obtained for single atom tips, while the intensity drops sharply for multi-atom tips. Adsorbing the CO molecule on a Cu adatom [CO/Cu/Cu(111)] such that it is elevated over the substrate strongly diminishes the tip dependence of IETS intensity, showing that an elevated position channels most of the tunneling current through the CO molecule even for multi-atom tips, while a large fraction of the tunneling current bypasses the CO molecule in the case of CO/Cu(111).

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22 Apr 16:09

Engineering the electronic bandgaps and band edge positions in carbon-substituted 2D boron nitride: a first-principles investigation. (arXiv:1504.05062v1 [cond-mat.mtrl-sci])

by Sharmila N. Shirodkar, Umesh V. Waghmare, Timothy S. Fisher, Ricardo Grau-Crespo

Modification of graphene to open a robust gap in its electronic spectrum is essential for its use in field effect transistors and photochemistry applications. Inspired by recent experimental success in the preparation of homogeneous alloys of graphene and boron nitride (BN), we consider here engineering the electronic structure and bandgap of C$_{2x}$B$_{1-x}$N$_{1-x}$ alloys via both compositional and configurational modification. We start from the BN end-member, which already has a large bandgap, and then show that (a) the bandgap can in principle be reduced to about 2 eV with moderate substitution of C $(x<0.25)$; and (b) the electronic structure of C$_{2x}$B$_{1-x}$N$_{1-x}$ can be further tuned not only with composition $x$, but also with the configuration adopted by C substituents in the BN matrix. Our analysis, based on accurate screened hybrid functional calculations, provides a clear understanding of the correlation found between the bandgap and the level of aggregation of C atoms: the bandgap decreases most when the C atoms are maximally isolated, and increases with aggregation of C atoms due to the formation of bonding and anti-bonding bands associated with hybridization of occupied and empty defect states. We determine the location of valence and conduction band edges relative to vacuum and discuss the implications on the potential use of 2D C$_{2x}$B$_{1-x}$N$_{1-x}$ alloys in photocatalytic applications. Finally, we assess the thermodynamic limitations on the formation of these alloys using a cluster expansion model derived from first-principles.

22 Apr 16:04

Site-dependent evolution of electrical conductance from tunneling to atomic point contact. (arXiv:1504.05494v1 [cond-mat.mes-hall])

by Howon Kim, Yukio Hasegawa

Using scanning tunneling microscopy (STM), we investigated the evolution of electrical conductance between a Pb tip and Pb(111) surface from tunneling to atomic point contact at a site that was defined with atomic precision. We found that the conductance evolution depended on the contact site, for instance, on-top, bridge, or hollow (hcp and fcc) sites in the Pb lattice. In the transition from tunneling to contact regimes, the conductance measured at the on-top site was enhanced. In the point contact regime, the hollow sites had conductances larger than those of the other sites, and between the hollow sites, the hcp site had a conductance larger than that of the fcc site. We also observed the enhancement and reversal of the apparent height in atomically resolved high-current STM images, consistent with the results of the conductance traces. Our results indicate the importance of atomic configuration in the conductance of atomic junctions and suggest that attractive chemical interactions have a significant role in electron transport between contacting atoms.

22 Apr 16:00

Ultrafast optical excitation of magnetic skyrmions

by N. Ogawa

Magnetic skyrmions in an insulating chiral magnet Cu2OSeO3 were studied by all-optical spin wave spectroscopy. The spins in the conical and skyrmion phases were excited by the impulsive magnetic field from the inverse-Faraday effect, and resultant spin dynamics were detected by using time-resolved magneto-optics. Clear dispersions of the helimagnon were observed, which is accompanied by a distinct transition into the skyrmion phase, by sweeping temperature and magnetic field. In addition to the collective excitations of skyrmions, i.e., rotation and breathing modes, several spin precession modes were identified, which would be specific to optical excitation. The ultrafast, nonthermal, and local excitation of the spin systems by photons would lead to the efficient manipulation of nano-magnetic structures.

Scientific Reports 5 doi: 10.1038/srep09552

22 Apr 15:57

Symmetry-protected topological order in magnetization plateau states of quantum spin chains

by Shintaro Takayoshi, Keisuke Totsuka, and Akihiro Tanaka

Author(s): Shintaro Takayoshi, Keisuke Totsuka, and Akihiro Tanaka

A symmetry-protected topologically ordered phase is a short-range entangled state, for which some imposed symmetry prohibits the adiabatic deformation into a trivial state which lacks entanglement. In this paper we argue that magnetization plateau states of one-dimensional antiferromagnets which sat...


[Phys. Rev. B 91, 155136] Published Wed Apr 22, 2015

22 Apr 15:54

Assembling molecular Sierpiński triangle fractals

by Jian Shang

Nature Chemistry 7, 389 (2015). doi:10.1038/nchem.2211

Authors: Jian Shang, Yongfeng Wang, Min Chen, Jingxin Dai, Xiong Zhou, Julian Kuttner, Gerhard Hilt, Xiang Shao, J. Michael Gottfried & Kai Wu

A series of molecular fractals, specifically Sierpiński triangles, can be assembled on a Ag(111) surface from small, bent oligophenyls with a bromo group at each end. The self-assembly is driven by the formation of synergistic halogen and hydrogen bonds between the molecular building blocks, and defect-free structures with more than 100 individual components are observed.

16 Apr 22:41

Cross-Coupling of Aryl-Bromide and Porphyrin-Bromide on an Au(111) Surface

by Guowen Kuang, Qiushi Zhang, Deng Yuan Li, Xue Song Shang, Tao Lin, Pei Nian Liu, Nian Lin

Abstract

Cross-coupling is of great importance in organic synthesis. Here it is demonstrated that cross-coupling of aryl-bromide and porphyrin-bromide takes place on a Au(111) surface in vacuo. The products are oligomers consisting of porphyrin moieties linked by p-phenylene at porphyrin’s meso-positions. The ratio of the cross-coupled versus homocoupled bonds can be regulated by the reactant concentrations. Kinetic Monte Carlo simulations were applied to determine the activation barrier. It is expected that this reaction can be employed in other aryl-bromide precursors for designing alternating co-polymers incorporating porphyrin and other functional moieties.

Thumbnail image of graphical abstract

Back on the chain gang: Aryl-bromide and porphyrin-bromide cross-coupling on an Au(111) surface with a yield as high as 95 % was achieved, as confirmed by submolecularly resolved scanning tunnelling microscopy imaging (see figure). Tuning the ratio of the two reactants allowed formation of 95 % of the cross-coupled bonds. The activation barriers were determined using kinetic Monte Carlo simulations.