: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

and Applications of Fullerenes, Carbon Dots, Nanotubes, Graphene, Nanodiamonds, and Combined Superstructures Vasilios Georgakilas,† Jason A. Perman,‡ Jiri Tucek,‡ and Radek Zboril*,‡ †Material Science Department, University of Patras, 26504 Rio Patras, Greece ‡Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacky University in Olomouc, 17 listopadu 1192/12, 771 46 Olomouc, Czech Republic

Broad family of carbon nanoallotropes: classification, chemistry, and applications of fullerenes, carbon dots, nanotubes, graphene, nanodiamonds, and combined superstructures.

The electronic properties of graphene, a two-dimensional crystal of carbon atoms, are exceptionally novel. For instance, the low-energy quasiparticles in graphene behave as massless chiral Dirac fermions which has led to the experimental observation of many interesting effects similar to those predicted in the relativistic regime. Graphene also has immense potential to be a key ingredient of new devices, such as single molecule gas sensors, ballistic transistors and spintronic devices. Bilayer graphene, which consists of two stacked monolayers and where the quasiparticles are massive chiral fermions, has a quadratic low-energy band structure which generates very different scattering properties from those of the monolayer. It also presents the unique property that a tunable band gap can be opened and controlled easily by a top gate. These properties have made bilayer graphene a subject of intense interest. In this review, we provide an in-depth description of the physics of monolayer and bilayer graphene f...

Properties of graphene: a theoretical perspective

The possibility that non-magnetic materials such as carbon could exhibit a novel type of s-p electron magnetism has attracted much attention over the years, not least because such magnetic order is predicted to be stable at high temperatures. It has been demonstrated that atomic-scale structural defects of graphene can host unpaired spins, but it remains unclear under what conditions long-range magnetic order can emerge from such defect-bound magnetic moments. Here we propose that, in contrast to random defect distributions, atomic-scale engineering of graphene edges with specific crystallographic orientation--comprising edge atoms from only one sub-lattice of the bipartite graphene lattice--can give rise to a robust magnetic order. We use a nanofabrication technique based on scanning tunnelling microscopy to define graphene nanoribbons with nanometre precision and well-defined crystallographic edge orientations. Although so-called 'armchair' ribbons display quantum confinement gaps, ribbons with the 'zigzag' edge structure that are narrower than 7 nanometres exhibit an electronic bandgap of about 0.2-0.3 electronvolts, which can be identified as a signature of interaction-induced spin ordering along their edges. Moreover, upon increasing the ribbon width, a semiconductor-to-metal transition is revealed, indicating the switching of the magnetic coupling between opposite ribbon edges from the antiferromagnetic to the ferromagnetic configuration. We found that the magnetic order on graphene edges of controlled zigzag orientation can be stable even at room temperature, raising hopes of graphene-based spintronic devices operating under ambient conditions.

/pdf/room-temperature-magnetic-order-on-zigzag-edges-of-narrow-1mvk6ez50g.pdf

Room-temperature magnetic order on zigzag edges of narrow graphene nanoribbons

A prerequisite for future graphene nanoribbon (GNR) applications is the ability to fine-tune the electronic band gap of GNRs. Such control requires the development of fabrication tools capable of precisely controlling width and edge geometry of GNRs at the atomic scale. Here we report a technique for modifying GNR band gaps via covalent self-assembly of a new species of molecular precursors that yields n = 13 armchair GNRs, a wider GNR than those previously synthesized using bottom-up molecular techniques. Scanning tunneling microscopy and spectroscopy reveal that these n = 13 armchair GNRs have a band gap of 1.4 eV, 1.2 eV smaller than the gap determined previously for n = 7 armchair GNRs. Furthermore, we observe a localized electronic state near the end of n = 13 armchair GNRs that is associated with hydrogen-terminated sp2-hybridized carbon atoms at the zigzag termini.

Tuning the band gap of graphene nanoribbons synthesized from molecular precursors

We determine the stability, the geometry, the electronic, and magnetic structure of hydrogen-terminated graphene-nanoribbon edges as a function of the hydrogen content of the environment by means of density functional theory. Antiferromagnetic zigzag ribbons are stable only at extremely low ultravacuum pressures. Under more standard conditions, the most stable structures are the mono- and dihydrogenated armchair edges and a zigzag edge reconstruction with one di- and two monohydrogenated sites. At high hydrogen concentration "bulk" graphene is not stable and spontaneously breaks to form ribbons, in analogy to the spontaneous breaking of graphene into small-width nanoribbons observed experimentally in solution. The stability and the existence of exotic edge electronic states and/or magnetism is rationalized in terms of simple concepts from organic chemistry (Clar's rule).

Structure, stability, edge states, and aromaticity of graphene ribbons.

We show that Clar's theory of the aromatic sextet is a simple and powerful tool to predict the stability, the \pi-electron distribution, the geometry, the electronic/magnetic structure of graphene nanoribbons with different hydrogen edge terminations. We use density functional theory to obtain the equilibrium atomic positions, simulated scanning tunneling microscopy (STM) images, edge energies, band gaps, and edge-induced strains of graphene ribbons that we analyze in terms of Clar formulas. Based on their Clar representation, we propose a classification scheme for graphene ribbons that groups configurations with similar bond length alternations, STM patterns, and Raman spectra. Our simulations show how STM images and Raman spectra can be used to identify the type of edge termination.

Clar's Theory, STM Images, and Geometry of Graphene Nanoribbons

We show that Clar’s theory of the aromatic sextet is a simple and powerful tool to predict the stability, the π-electron distribution, the geometry, and the electronic/magnetic structure of graphene nanoribbons with different hydrogen edge terminations. We use density functional theory to obtain the equilibrium atomic positions, simulated scanning tunneling microscopy (STM) images, edge energies, band gaps, and edge-induced strains of graphene ribbons that we analyze in terms of Clar formulas. On the basis of their Clar representation, we propose a classification scheme for graphene ribbons that groups configurations with similar bond length alternations, STM patterns, and Raman spectra. Our simulations show how STM images and Raman spectra can be used to identify the type of edge termination.

Clar’s Theory, π-Electron Distribution, and Geometry of Graphene Nanoribbons

We determine, by means of density functional theory, the stability and the structure of graphene nanoribbon (GNR) edges in presence of molecules such as oxygen, water, ammonia, and carbon dioxide. As in the case of hydrogen-terminated nanoribbons, we find that the most stable armchair and zigzag configurations are characterized by a non-metallic/non-magnetic nature, and are compatible with Clar's sextet rules, well known in organic chemistry. In particular, we predict that, at thermodynamic equilibrium, neutral GNRs in oxygen-rich atmosphere should preferentially be along the armchair direction, while water-saturated GNRs should present zigzag edges. Our results promise to be particularly useful to GNRs synthesis, since the most recent and advanced experimental routes are most effective in water and/or ammonia-containing solutions.

/pdf/structure-and-stability-of-graphene-nanoribbons-in-oxygen-4v62c8nbfb.pdf

Structure and stability of graphene nanoribbons in oxygen, carbon dioxide, water, and ammonia

We determine the stability, the geometry, the electronic, and magnetic structure of hydrogen-terminated graphene-nanoribbon edges as a function of the hydrogen content of the environment by means of density functional theory. Antiferromagnetic zigzag ribbons are stable only at extremely low ultravacuum pressures. Under more standard conditions, the most stable structures are the mono- and dihydrogenated armchair edges and a zigzag edge reconstruction with one di- and two monohydrogenated sites. At high hydrogen concentration \"bulk\" graphene is not stable and spontaneously breaks to form ribbons, in analogy to the spontaneous breaking of graphene into small-width nanoribbons observed experimentally in solution. The stability and the existence of exotic edge electronic states and/or magnetism is rationalized in terms of simple concepts from organic chemistry (Clar's rule).

http://absimage.aps.org/image/MAR09/MWS_MAR09-2008-004307.pdf

Tobias Wassmann

Papers

Structure, stability, edge states, and aromaticity of graphene ribbons.

Clar's Theory, STM Images, and Geometry of Graphene Nanoribbons

Clar’s Theory, π-Electron Distribution, and Geometry of Graphene Nanoribbons

Structure and stability of graphene nanoribbons in oxygen, carbon dioxide, water, and ammonia

Structure, Stability, Edge States and Aromaticity of Graphene Ribbons