Charge-transfer optical absorption mechanism of DNA:Ag-nanocluster complexes.

Optical properties of DNA:Ag-nanoclusters complexes have been successfully applied experimentally in Chemistry, Physics, and Biology. Nevertheless, the mechanisms behind their optical activity remain unresolved. In this work, we present a time-dependent density functional study of optical absorption in DNA:Ag_{4}. In all 23 different complexes investigated, we obtain new absorption peaks in the visible region that are not found in either the isolated Ag_{4} or isolated DNA base pairs. Absorption from red to green are predominantly of charge-transfer character, from the Ag_{4} to the DNA fragment, while absorption in the blue-violet range are mostly associated to electronic transitions of a mixed character, involving either DNA-Ag_{4} hybrid orbitals or intracluster orbitals. We also investigate the role of exchange-correlation functionals in the calculated optical spectra. Significant differences are observed between the calculations using the PBE functional (without exact exchange) and the CAM-B3LYP functional (which partly includes exact exchange). Specifically, we observe a tendency of charge-transfer excitations to involve purines bases, and the PBE spectra error is more pronounced in the complexes where the Ag cluster is bound to the purines. Finally, our results also highlight the importance of adding both the complementary base pair and the sugar-phosphate backbone in order to properly characterize the absorption spectrum of DNA:Ag complexes.

Magnetic properties of C-N planar structures: d(0) ferromagnetism and half-metallicity.

We investigate, from first principles calculations, the magnetic properties of planar carbon nitride structures with the lowest formation energies within twenty eight distinct stoichiometries and porosities. Surprisingly, we find that 3/4 of the low-energy carbon nitride structures present energetically favorable magnetic phases, and that more than 3/10 are ferromagnetic. This suggests that d(0) magnetism is a usual feature in this class of materials. Notably, within the energetically favorable ferromagnetic structures, we find that two structures have very high stabilization energies for ferromagnetic order, one having the highest predicted so far for this class of materials. We also find that several structures are half-metals, and one structure is half-zero-gap semiconductor (semicondutor in one spin channel, and graphene-like in the other channel).

Electronic confinement in graphene ruled by N doped extended defects.

We investigate by means of ab-initio simulations the formation energy and the electronic properties of substitutional N doping in graphene with distinct grain boundary defects as a function of the N concentration. Our results show that the presence of substitutional N atoms along the defective regions is quite likely for several N concentrations. Also, we find either semiconducting or metallic structures, depending on the N concentration. Confinement effects were also investigated for the semiconducting structures. We find that the distance between the defect lines can modulate the band structure of those semiconducting N doped lines. This opens an interesting possibility to produce two-dimensional heterojunctions composed by N doped grain boundaries with different distances between the defect lines.

Graphene­boron nitride superlattices: the role of point defects at the BN layer.

We investigate, by means of first-principles calculations, the role of hBN point defects on the energetical stability and electronic structure of heterostructures composed of graphene atop hBN, rotated at angles of 13.17°, 9.43° and 7.34°. We consider, as possible point defects, boron and nitrogen vacancies and antisites, substitutional oxygen at the nitrogen site ON, substitutional carbon dimers, and nitrogen interstitials. The electronic and structural properties of all defects were analyzed. Among these, the most stable is ON, with negative formation energies at several possible rotation angles and chemical environments. Under such conditions, ON doping can raise the Fermi level of the neutral system by as much as 1 eV relative to graphene's Dirac point, reaching the band crossing between adjacent Dirac cones at the M point of the heterostructure Brillouin zone. This could lead to interesting electronic transport properties without the need for electrostatic doping.

In situ atomic force microscopy tip-induced deformations and Raman spectroscopy characterization of single-wall carbon nanotubes.

In this work, an atomic force microscope (AFM) is combined with a confocal Raman spectroscopy setup to follow in situ the evolution of the G-band feature of isolated single-wall carbon nanotubes (SWNTs) under transverse deformation. The SWNTs are pressed by a gold AFM tip against the substrate where they are sitting. From eight deformed SWNTs, five exhibit an overall decrease in the Raman signal intensity, while three exhibit vibrational changes related to the circumferential symmetry breaking. Our results reveal chirality dependent effects, which are averaged out in SWNT bundle measurements, including a previously elusive mode symmetry breaking that is here explored using molecular dynamics calculations.

Anomalous response of supported few-layer hexagonal boron nitride to DC electric fields: a confined water effect?

We use electric force microscopy (EFM) to study the response of supported few-layer hexagonal boron nitride (h-BN) to an electric field applied by the EFM tip. Our results show an anomalous behavior in the dielectric response of h-BN atop Si oxide for different bias polarities: for a positive bias applied to the tip, h-BN layers respond with a larger dielectric constant than the dielectric constant of the substrate, while for a negative bias, the h-BN dielectric constant appears to be smaller. Based on ab initio calculations, we propose that this behavior is due to a water layer confined between the Si oxide substrate and h-BN layers. This hypothesis was experimentally confirmed by sample annealing and also by a comparative analysis with h-BN on a non-polar substrate.

First-principles investigation of electrochemical properties of gold nanoparticles.

A first-principles formalism is employed to investigate the effects of size and structure on the electronic and electrochemical properties of Au nanoparticles with diameters between 0.8 and 2.0 nm. We find that the behavior of the ionization potentials (IPs) and the electron affinities (EAs) as a function of cluster size can be separated into many-body and single-electron contributions. The many-body part is only (and continuously) dependent on particle size, and can be very well described in terms of the capacitance of classical spherical conductors for clusters with more the 55 atoms. For smaller clusters, molecule-like features lead the capacitance and fundamental gap to differ systematically from those of a classical conductor with decreasing size. The single-electron part fluctuates with particle structure. Upon calculating the neutral chemical potential micro(0) = (IP+EA)/2, the many-body contributions cancel out, resulting in fluctuations of micro(0) around the bulk Au work function, consistent with experimental results. The values of IP and EA changes upon functionalization with thiolated molecules, and the magnitude of the observed changes does not depend on the length of the alkane chain. The functionalization can also lead to a transition from metallic to non-metallic behavior in small nanoparticles, which is consistent with experimental observations.

Universal response of single-wall carbon nanotubes to radial compression.

The mechanical response of single-wall carbon nanotubes to radial compression is investigated via atomic force microscopy (AFM). We find that the force F applied by an AFM tip (with radius R) onto a nanotube (with diameter d), rescaled through the quantity Fd;{3/2}(2R);{-1/2}, falls into a universal curve as a function of the compressive strain. Such universality is reproduced analytically in a model where the graphene bending modulus is the only fitting parameter. The application of this model to the radial Young's modulus E_{r} leads to a further universal-type behavior which explains the large variations of nanotube E_{r} reported in the literature.

Deformation induced semiconductor-metal transition in single wall carbon nanotubes probed by electric force microscopy.

We report the direct experimental observation of the semiconductor-metal transition in single-wall carbon nanotubes (SWNTs) induced by compression with the tip of an atomic force microscope. This transition is probed via electric force microscopy by monitoring SWNT charge storage. Experimental data show that such charge storage is different for metallic and semiconducting SWNTs, with the latter presenting a strong dependence on the tip-SWNT force during injection. Ab initio calculations corroborate experimental observations and their interpretation.

Surface dangling-bond States and band lineups in hydrogen-terminated Si, Ge, and Ge/si nanowires.

We report an ab initio study of the electronic properties of surface dangling-bond (SDB) states in hydrogen-terminated Si and Ge nanowires with diameters between 1 and 2 nm, Ge/Si nanowire heterostructures, and Si and Ge (111) surfaces. We find that the charge transition levels epsilon(+/-) of SDB states behave as a common energy reference among Si and Ge wires and Si/Ge heterostructures, at 4.3+/-0.1 eV below the vacuum level. Calculations of epsilon(+/-) for isolated atoms indicate that this nearly constant value is a periodic-table atomic property.

Structures of Si and Ge nanowires in the subnanometer range.

We report an ab initio investigation of several structures of pristine Si and Ge nanowires with diameters between 0.5 and 2.0 nm. We consider nanowires based on the diamond structure, high-density bulk structures, and fullerenelike structures. Our calculations indicate a transition from sp3 geometries to structures with higher coordination, for diameters below 1.4 nm. We find that diamond-structure nanowires are unstable for diameters smaller than 1 nm, undergoing considerable structural transformations towards amorphouslike wires. For diameters between 0.8 and 1 nm, filled-fullerene wires are the most stable. For even smaller diameters (approximately 0.5 nm), we find that a simple hexagonal structure is particularly stable for both Si and Ge.

Asymmetric line shape in the emission spectra of conjugated polymer thin films: an experimental signature of one-dimensional electronic states.

The photoluminescence (PL) properties of thin films of the conjugated polymer [poly(2,5-bis(2(')-ethyl-hexyl)-1,4-phenylenevinylene] have been investigated. At low temperatures the PL spectra show a narrow peak for the electronic transition and a series of well defined vibronic sidebands, which clearly reveal the electron coupling with two different vibronic modes. The purely electronic transition peak is observed to be very asymmetric so that it cannot be adjusted by a single Lorentzian or Gaussian function. In order to understand and explain this asymmetry we have considered a model where the purely electronic transition line shape is partially generated by a broadened square-root singularity representing one-dimensional electron states, and partially by localized (zero-dimensional) states. The localized states are assumed to be those very close to the band edges and are represented in our model by a single Gaussian function. Numerical Franck-Condon analysis was performed, resulting in a very good agreement between the theoretical and the experimental emission spectra. This procedure has confirmed the one-dimensional character of the electron states as the basis for the understanding of the purely electronic line shape asymmetry in the PL spectra of conjugated polymers at low temperatures.

Small polarons in dry DNA.

We report ab initio calculations for positively charged fragments of dry poly(dC)-poly(dG) DNA, with up to 4 C-G pairs. We find a strong hole-lattice coupling and clear evidence for the formation of small polarons. The largest geometry distortions occur in only one or two base pairs. They involve the stretching of weak bonds within each base pair, increasing the distance of positive hydrogens, and decreasing that of negative oxygens, to the region in which the hole localizes. We obtain an energy of approximately 0.30 eV for the polaron formation, nearly independent of the chain size. From it, we can estimate an activation energy for polaron hopping of approximately 0.15 eV, consistent with the available experimental value.

Polarons in carbon nanotubes.

We use ab initio total-energy calculations to predict the existence of polarons in semiconducting carbon nanotubes (CNTs). We find that the CNTs' band edge energies vary linearly and the elastic energy increases quadratically with both radial and with axial distortions, leading to the spontaneous formation of polarons. Using a continuum model parametrized by the ab initio calculations, we estimate electron and hole polaron lengths, energies, and effective masses and analyze their complex dependence on CNT geometry. Implications of polaron effects on recently observed electro- and optomechanical behavior of CNTs are discussed.

Instabilities in diamond under high shear stress

We investigate, through first-principles calculations, lattice instabilities induced in diamond by the application of high shear stresses. For shear stresses as low as 95 GPa a lattice instability will occur, leading to graphitelike layered structures. This effect is highly anisotropic. The reversal of the direction of the applied shear forces may cause a change of 80 GPa in the shear stress value at which the instability develops. The same reversal also causes different bonds to be broken, resulting in a drastic change in the orientation of the resulting graphitelike structures. We also find that an additional compressive stress of 50 GPa along the (111) direction does not eliminate the shear-induced instability.