Optical absorption in small BN and C nanotubes

We present a theoretical study of the optical absorption spectrum of small boron-nitride and carbon nanotubes using time-dependent density-functional theory and the random phase approximation. Both for C and BN tubes, the absorption of light polarized perpendicular to the tube-axis is strongly suppressed due to local field effects. Since BN-tubes are wide band-gap insulators, they only absorb in the ultra-violet energy regime, independently of chirality and diameter. In comparison with the spectra of the single C and BN-sheets, the tubes display additional fine-structure which stems from the (quasi-) one-dimensionality of the tubes and sensitively depends on the chirality and tube diameter. This fine structure can provide additional information for the assignment of tube indices in high resolution optical absorption spectroscopy.Comment: 5 pages, 3 figure

The design of aircraft using the decision support problem technique

The Decision Support Problem Technique for unified design, manufacturing and maintenance is being developed at the Systems Design Laboratory at the University of Houston. This involves the development of a domain-independent method (and the associated software) that can be used to process domain-dependent information and thereby provide support for human judgment. In a computer assisted environment, this support is provided in the form of optimal solutions to Decision Support Problems

Spectrophotometry of thin films of light absorbing particles

Thin films of dispersions of light absorbing solid particles or emulsions containing a light absorbing solute all have a non-uniform distribution of light absorbing species throughout the sample volume. This results in non-uniform light absorption over the illuminated area which causes the optical absorbance, as measured using a conventional specular UV-vis spectrophotometer, to deviate from the Beer-Lambert relationship. We have developed a theoretical model to account for the absorbance properties of such films which are shown to depend on the size and volume fraction of the light absorbing particles plus other sample variables. We have compared model predictions with measured spectra for samples consisting of emulsions containing a dissolved light absorbing solute. Using no adjustable parameters, the model successfully predicts the behaviour of non-uniform, light absorbing emulsion films with varying values of droplet size, volume fraction and other parameters

Ab initio study of the optical absorption and wave-vector-dependent dielectric response of graphite

We performed ab initio calculations of the optical absorption spectrum and the wave-vector-dependent dielectric and energy-loss functions of graphite in the framework of the random-phase approximation. In the absorption spectrum, the most prominent peaks were analyzed in terms of interband transitions from specific regions of the Brillouin zone. The inclusion of the crystal local-field effects (LFE) in the response had an important influence on the absorption spectrum for light polarization parallel to the c axis. The calculated electron energy-loss spectra, even without LFE, were in very good agreement with existing momentum-dependent energy-loss experiments concerning the peak positions of the two valence-electron plasmons. Important aspects of the line shape and anisotropy of the energy-loss function at large momentum transfer q were also well described: the splitting of the total (π+σ) plasmon and the appearance of peaks originating from interband transitions. Finally, the role of the interlayer interaction was studied, in particular with regard to its effect on the absorption spectrum for light polarization parallel to c, and to the position of the higher-frequency π+σ plasmon.This work was supported by the EC-RTN program NANOPHASE (Contract No. HPRN-CT-2000-00167). A.R. acknowledges support from the Ecole Polytechnique during a sabbatical leave in 2001 where this work was started and partial support from Spanish MCyT(MAT2001-0946), University of the Basque Country (9/UPV 00206.215-13639/2001) and COMELCAN (HPRN-CT-2000-00128). Computer time was granted by IDRIS (Project No. 544).Peer reviewe

Evaporation of particle-stabilised emulsion sunscreen films

We recently showed (Binks et al., ACS Appl. Mater. Interfaces, 2016, DOI: 10.1021/acsami.6b02696) how evaporation of sunscreen films consisting of solutions of molecular UV filters leads to loss of UV light absorption and derived sun protection factor (SPF). In the present work, we investigate evaporation-induced effects for sunscreen films consisting of particle-stabilized emulsions containing a dissolved UV filter. The emulsions contained either droplets of propylene glycol (PG) in squalane (SQ), droplets of SQ in PG or droplets of decane in PG. In these different emulsion types, the SQ is involatile and shows no evaporation, the PG is volatile and evaporates relatively slowly, whereas the decane is relatively very volatile and evaporates quickly. We have measured the film mass and area, optical micrographs of the film structure, and the UV absorbance spectra during evaporation. For emulsion films containing the involatile SQ, evaporation of the PG causes collapse of the emulsion structure with some loss of specular UV absorbance due to light scattering. However, for these emulsions with droplets much larger than the wavelength of light, the light is scattered only at small forward angles so does not contribute to the diffuse absorbance and the film SPF. The UV filter remains soluble throughout the evaporation and thus the UV absorption by the filter and the SPF remain approximately constant. Both PG-in-SQ and SQ-in-PG films behave similarly and do not show area shrinkage by dewetting. In contrast, the decane-in-PG film shows rapid evaporative loss of the decane, followed by slower loss of the PG resulting in precipitation of the UV filter and film area shrinkage by dewetting which cause the UV absorbance and derived SPF to decrease. Measured UV spectra during evaporation are in reasonable agreement with spectra calculated using models discussed here

Anomalous Angular Dependence of the Dynamic Structure Factor near Bragg Reflections: Graphite

The electron energy-loss function of graphite is studied for momentum transfers q beyond the first Brillouin zone. We find that near Bragg reflections the spectra can change drastically for very small variations in q. The effect is investigated by means of first principle calculations in the random phase approximation and confirmed by inelastic x-ray scattering measurements of the dynamic structure factor S(q,\omega). We demonstrate that this effect is governed by crystal local field effects and the stacking of graphite. It is traced back to a strong coupling between excitations at small and large momentum transfers

Optical absorption and electron energy loss spectra of carbon and boron nitride nanotubes: a first-principles approach

arXiv:cond-mat/0308126We present results for the optical absorption spectra of small-diameter single-walled carbon and boron nitride nanotubes obtained by ab initio calculations in the framework of time-dependent density-functional theory. We compare the results with those obtained for the corresponding layered structures, i.e. the graphene and hexagonal boron nitride sheets. In particular, we focus on the role of depolarization effects, anisotropies, and interactions in the excited states. We show that the random phase approximation reproduces well the main features of the spectra when crystal local field effects are correctly included, and discuss to what extent the calculations can be further simplified by extrapolating results obtained for the layered systems to results expected for the tubes. The present results are relevant for the interpretation of data obtained by recent experimental tools for nanotube characterization, such as optical and fluorescence spectroscopies, as well as polarized resonant Raman scattering spectroscopy. We also address electron energy loss spectra in the small-q momentum-transfer limit. In this case, the interlayer and intertube interactions play an enhanced role with respect to optical spectroscopy.This work was supported by the European Community Research Training Networks NANOPHASE (HPRN-CT-2000-00167), COMELCAN (HPRN-CT-2000-00128), and M-DNA (IST-2001-38051), by the French Ministère de la Recherche through the project NABOCO (Programme No.MPH 724 D), by the SpanishMCyT (MAT2001- 0946), and by the University of the Basque Country (9/UPV 00206.215- 13639/2001). The computer time was granted by IDRIS (Project No. 544), DIPC, and CEPBA (Barcelona).Peer Reviewe

The prismatic Sigma 3 (10-10) twin bounday in alpha-Al2O3 investigated by density functional theory and transmission electron microscopy

The microscopic structure of a prismatic $\Sigma 3$ $(10\bar{1}0)$ twin boundary in \aal2o3 is characterized theoretically by ab-initio local-density-functional theory, and experimentally by spatial-resolution electron energy-loss spectroscopy in a scanning transmission electron microscope (STEM), measuring energy-loss near-edge structures (ELNES) of the oxygen $K$-ionization edge. Theoretically, two distinct microscopic variants for this twin interface with low interface energies are derived and analysed. Experimentally, it is demonstrated that the spatial and energetical resolutions of present high-performance STEM instruments are insufficient to discriminate the subtle differences of the two proposed interface variants. It is predicted that for the currently developed next generation of analytical electron microscopes the prismatic twin interface will provide a promising benchmark case to demonstrate the achievement of ELNES with spatial resolution of individual atom columns

How the sun protection factor (SPF) of sunscreen films change during solar irradiation

We have investigated how the sun protection factor (SPF) of different types of sunscreen film varies with “standard” solar irradiation due to photochemical processes. We have used a combination of chemical actinometry, measurement and modelling to estimate the overall quantum yields for the photoprocesses occurring for avobenzone (AVB) and isopentyl p-methoxycinnamate (MC) in either propane-1,2-diol (PG) or squalane (SQ) as solvent. Using the obtained parameters, we have developed models to calculate the evolution of the film spectra and derived SPF values for both non-scattering sunscreen films consisting of solutions of multiple UV filters and for highly scattering Pickering emulsion based sunscreen films. Model calculations for all films are in excellent agreement with film spectra measured as a function of irradiation time using different laboratory light sources. Finally, using the estimated parameters and experimentally validated models, we are able to quantitatively predict how the in vitro SPF values for different film types containing any set combination of UV filter concentrations will vary with time due to photochemical processes induced by irradiation with “standard” sunlight. This provides a useful tool for the rational design and optimisation of new sunscreen formulations

Linear plasmon dispersion in single-wall carbon nanotubes and the collective excitation spectrum of graphene

We have measured a strictly linear pi-plasmon dispersion along the axis of individualized single wall carbon nanotubes, which is completely different from plasmon dispersions of graphite or bundled single wall carbon nanotubes. Comparative ab initio studies on graphene based systems allow us to reproduce the different dispersions. This suggests that individualized nanotubes provide viable experimental access to collective electronic excitations of graphene, and it validates the use of graphene to understand electronic excitations of carbon nanotubes. In particular, the calculations reveal that local field effects (LFE) cause a mixing of electronic transitions, including the 'Dirac cone', resulting in the observed linear dispersion