Optimizing Growth Conditions for Coaxial Multi-Walled Carbon Nanotubes

Coaxial multi-walled carbon nanotubes have a multi-layered structure in which a core multi-walled carbon nanotube is grown inside a sheath multi-walled nanotube from a metal-catalyst nanoparticle. In this paper, we report the optimum conditions to grow coaxial multi-walled carbon nanotubes by chemical vapor deposition. The coaxial nanotubes are studied by means of transmission electron microscopy to reveal their crystallinity and morphology. Our results show that chemical vapor deposition growth at around 1000°C with a 0.04–0.07 mg/cm^3 dose of palmitic acid yields the best result

A Structure-free Method for Quantifying Conformational Flexibility in proteins

All proteins sample a range of conformations at physiologic temperatures and this inherent flexibility enables them to carry out their prescribed functions. A comprehensive understanding of protein function therefore entails a characterization of protein flexibility. Here we describe a novel approach for quantifying a protein’s flexibility in solution using small-angle X-ray scattering (SAXS) data. The method calculates an effective entropy that quantifies the diversity of radii of gyration that a protein can adopt in solution and does not require the explicit generation of structural ensembles to garner insights into protein flexibility. Application of this structure-free approach to over 200 experimental datasets demonstrates that the methodology can quantify a protein’s disorder as well as the effects of ligand binding on protein flexibility. Such quantitative descriptions of protein flexibility form the basis of a rigorous taxonomy for the description and classification of protein structure.Massachusetts Institute of Technology (Steve G. and Renee Finn Faculty Innovation Fellowship)Swiss National Science Foundation (Early Postdoc.Mobility Fellowship

An MS-CASPT2 Study of the Photodecomposition of 4- Methoxyphenyl Azide. Role of Internal Conversion and Intersystem Crossing

Aryl azides photochemistry is strongly dependent on the substituent relative position, as has been studied by time resolved resonant Raman (TR3) spectroscopy for 4-methoxyphenyl azide and its isomer 3-methoxyphenyl azide. When irradiated at 266 nm, the former results in 4,4’-dimethoxyazobenzene whereas the latter forms 1,2-didehydroazepine. It is proposed that the key step of the reactions is the formation of a nitrene derivative. Recently, it has been proposed by us that nitrenes might have a relevant role in the Surface-Enhanced Raman Scattering (SERS) of p-aminothiophenol, however, the molecular mechanism is not well known in neither of these cases. Therefore, we studied the photodecomposition of 4-methoxyphenyl azide using multiconfigurational self-consistent field methods (MC-SCF) with the CAS-SCF and MS-CASPT2 approximations and calculated the resonant Raman spectra of the relevant species using a multi-state version of Albrecht’s vibronic theory. The results propose that the reaction follows a two steps sequence after irradiation at 266 nm: an intersystem crossing 21A’/23A’’ which decays through a 21A’/21A’’ conical intersection producing molecular nitrogen and triplet 4-methoxyphenyl nitrene in its ground state.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Metastable anisotropy orientation of nematic quantum Hall fluids

We analyze the experimental observation of metastable anisotropy resistance orientation at half filled quantum Hall fluids by means of a model of a quantum nematic liquid in an explicit symmetry breaking potential. We interpret the observed ``rotation'' of the anisotropy axis as a process of nucleation of nematic domains and compute the nucleation rate within this model. By comparing with experiment, we are able to predict the critical radius of nematic bubbles, $R_c\sim 2.6 \mu m$. Each domain contains about $10^4$ electrons.Comment: 10 pages, 8 figures, final version as will appear in PR

Modeling the effect of the electrode potential in SERS by electronic structure calculations.

Surface Enhanced Raman Spectroscopy (SERS), due to the ability of greatly intensify the weak Raman signal of molecules adsorbed to metal surfaces, has proven to be a very useful tool to investigate changes in the electronic structure of metal-molecule surface complex. A deep knowledge of the electronic structure of these metal-molecule hybrid systems is key in electrochemistry, catalysis, plasmonics, molecular electronics, and in the development of selective and ultra-sensitive analytical sensors. The origin of this huge enhancement in SERS is due to two contributions: the electromagnetic (EM), related to surface plasmons, and the chemical mechanism, due to resonant charge transfer (CT) process between the adsorbate and the metal (CTSERS). Unfortunately, the SERS implies very complex phenomena where the molecule and the metal nanoparticle are involved. This fact makes challenging to build realistic theoretical models that take into account both the metal and the molecule at quantum level. We propose a methodology, based on DFT and ab initio electronic calculations, to simulate the effect of the electrode potential on the absorption, on the charge transfer states energies, and on the electronic excitations in metal-molecule hybrid systems from a microscopic point of view. This methodology consists on the prediction of Raman intensities from ab initio calculations of the geometries or the energy gradients at the excited states Franck-Condon point, bringing the possibility to predict the intensities in CTSERS as well as in resonance Raman without the need to know the excited state geometries, not always feasible to compute. The microscopic model adopted to mimic the effect of the interphase electric potential consist in a molecule adsorbed to a linear silver cluster [Agn-Adsorbate]q, were n is the number of silver atoms, and the total charge of the system (q) is zero for n=2 and q=±1 for n=1, 3 and 7.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Infrared Optical Properties of Amorphous and Nanocrystalline Ta2O5 Thin Films

The optical constants of tantalum pentoxide (Ta 2O5) are determined in a broad spectral region from the visible to the far infrared. Ta 2O5 films of various thicknesses from approximately 170 to 1600 nm aredeposited using reactive magnetron sputtering on Si substrates. X-ray diffraction shows that the as-deposited films are amorphous, and annealing in air at 800 °C results in the formation of nanocrystallineTa 2O5. Ellipsometry is used to obtain the dispersion in the visible and near-infrared. Two Fourier-transform infrared spectrometers are used to measure the transmittance and reflectance at wavelengths from 1 to 1000 μm. The surface topography and microstructure of the samples are examined using atomic force microscopy, confocal microscopy, and scanning electron microscopy. Classical Lorentz oscillatorsare employed to model the absorption bands due to phonons and impurities. A simple model is introduced to account for light scattering in the annealed films, which contain micro-cracks. For the unannealed samples, an effective-medium approximation is used to take into account the adsorbed moisture in the film and a Drude free-electron term is also added to model the broad background absorption

Study of the mechanical behavior of asphalt mixtures using fractional rheology to model their viscoelasticity

This study focuses on the mechanical behavior of asphalt mixtures composed of aggregate particles attached with an asphalt binder. Asphalt mixtures are viscoelastic composite materials widely used in the construction of pavement layers. The modelling of such materials is currently done using the Burgers model. However, this model is limited when explaining some of the viscoelastic phenomena of an asphalt mixture, mainly because the Burgers model was developed for a single material with a dual nature. This work presents a new approach that provides a more appropriate framework for studying asphalt mixtures. The model assumes an aggregate particle enclosed by an asphalt material. Viscoelastic equations were developed using derivatives of fractional order. Then, the creep, recovery, and relaxation phenomena in an asphalt mixture were analyzed using the new model. Unlike the Burgers model, the new model can predict the elastic jump observed at the beginning of the creep modulus. Thus, the new model seems to describe better those practical cases of asphalt mixtures used in the construction of pavement layers. The new model can be used to modify the properties of the binder for designing optimized and more resistant asphalt mixtures

Supersymmetric formulation of multiplicative white--noise stochastic processes

We present a supersymmetric formulation of Markov processes, represented by a family of Langevin equations with multiplicative white-noise. The hidden symmetry encodes equilibrium properties such as fluctuation-dissipation relations. The formulation does not depend on the particular prescription to define the Wiener integral. In this way, different equilibrium distributions, reached at long times for each prescription, can be formally treated on the same footing.Comment: 5 pages, no figures, version published in Phys. Rev.