Stretching of BDT-gold molecular junctions: thiol or thiolate termination?

It is often assumed that the hydrogen atoms in the thiol groups of a benzene-1,4-dithiol dissociate when Au-benzene-1,4-dithiol-Au junctions are formed. We demonstrate, by stability and transport property calculations, that this assumption cannot be made. We show that the dissociative adsorption of methanethiol and benzene-1,4-dithiol molecules on a flat Au(111) surface is energetically unfavorable and that the activation barrier for this reaction is as high as 1 eV. For the molecule in the junction, our results show, for all electrode geometries studied, that the thiol junctions are energetically more stable than their thiolate counterparts. Due to the fact that density functional theory (DFT) within the local density approximation (LDA) underestimates the energy difference between the lowest unoccupied molecular orbital and the highest occupied molecular orbital by several electron-volts, and that it does not capture the renormalization of the energy levels due to the image charge effect, the conductance of the Au-benzene-1,4-dithiol-Au junctions is overestimated. After taking into account corrections due to image charge effects by means of constrained-DFT calculations and electrostatic classical models, we apply a scissor operator to correct the DFT energy level positions, and calculate the transport properties of the thiol and thiolate molecular junctions as a function of the electrode separation. For the thiol junctions, we show that the conductance decreases as the electrode separation increases, whereas the opposite trend is found for the thiolate junctions. Both behaviors have been observed in experiments, therefore pointing to the possible coexistence of both thiol and thiolate junctions. Moreover, the corrected conductance values, for both thiol and thiolate, are up to two orders of magnitude smaller than those calculated with DFT-LDA. This brings the theoretical results in quantitatively good agreement with experimental data.

Effects of Temperature on Intraspecific Competition in Ectotherms

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Random regression models using different functions to model milk flow in dairy cows

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Evaluation of roof slope and exposure with different roofing materials in reduced models of animal production facilities in spring and summer

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Aplicação da análise de séries temporais para detecção e prognóstico de danos em estruturas inteligentes

Pós-graduação em Engenharia Mecânica - FEIS

Terminalia catappa L.: A medicinal plant from the Caribbean pharmacopeia with anti-Helicobacter pylori and antiulcer action in experimental rodent models

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effects of andiroba (Carapa guianensis) oil in ticks: ultrastructural analysis of the synganglion of Rhipicephalus sanguineus (Latreille, 1806) (Acari: Ixodidae)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Random regression models for milk, fat and protein in Colombian Buffaloes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Genetic analysis of the temperament of Nellore cattle using linear and threshold models

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A study of the errors of the averaged models in the restricted three-body problem in a short time scale

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Genotype x environment interaction for age at first calving, scrotal circumference, and yearling weight in Nellore cattle using reaction norms in multitrait random regression models

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Dynamic analysis for different finite element models of beams with viscoelastic damping layer

Many new viscoelastic materials have been developed recently to help improve noise and vibration levels in mechanical structures for applications in automobile and aeronautical industry. The viscoelastic layer treatment applied to solid metal structures modifies two main properties which are related to the mass distribution and the damping mechanism. The other property controlling the dynamics of a mechanical system is the stiffness that does not change much with the viscoelastic material. The model of such system is usually complex, because the viscoelastic material can exhibit nonlinear behavior, in contrast with the many available tools for linear dynamics. In this work, the dynamic behavior of sandwich beam is modeled by finite element method using different element types which are then compared with experimental results developed in the laboratory for various beams with different viscoelastic layer materials. The finite element model is them updated to help understand the effects in the damping for various natural frequencies and the trade-off between attenuation and the mass add to the structure.

An investigation into the effects of resonances on the time delay estimate for leak detection in buried plastic water distribution pipes

In water distribution systems, old metallic pipes have been replaced by plastic pipes due to their deterioration over time. Although acoustic methods are effective in finding leaks in metallic pipes, they have been found to be problematic when applied to plastic pipes due to the high damping within the pipe wall and the surrounding medium. This is responsible for the leak signal not traveling long distances. Moreover, the leak energy in plastic pipes is generally located at a narrow frequency range located at low frequencies. However, the presence of resonances can narrow even more this frequency range. In order to minimise the influence of background noise and resonances on the calculation of the time delay estimate, band-pass filters are often used to supress undesirable frequency components of the noise. The objective of this paper is to investigate the influence of resonances in the pipe system (pipe, valves, connections and hydrants), on the time delay estimate calculated using acoustic signals. Analytical models and actual leak data collected in a bespoke rig located in the United Kingdom are used to investigate this feature.

IR-visible upconversion and thermal effects in Pr3+/Yb3+-codoped Ga2O3 : La2S3 chalcogenide glasses

IR-visible upconversion fluorescence spectroscopy and thermal effects in pr(3+)/Yb3+-codoped Ga2O3:La2S3 chalcogenide glasses excited at 1.064 mum is reported. Intense visible upconversion emission in the wavelength region of 480-680 nm peaked around 500, 550, 620 and 660 nm is observed. Upconversion excitation of the Pr3+ excited-state visible emitting levels is achieved by st combination of phonon-assisted absorption, energy-transfer and phonon-assisted excited-state absorption processes. A threefold upconversion emission enhancement induced by thermal effects when the codoped sample was heated in the temperature range of 20-200 degreesC is demonstrated. The thermal-induced enhancement is attributed to a multiphonon-assisted anti-Stokes process which takes place in the excitation of the ytterbium and excited-state absorption of the praseodymium. The thermal effect is modelled by conventional rate equations considering temperature-dependent effective absorption cross-sections for the F-2(7/2)-F-2(5/2) ytterbium transition and (1)G(4)-P-3(0) praseadymium excited-state absorption, and it is shown to agree very well with experimental results. Frequency upconversion in singly Pr3+-doped samples pumped at 836 nm and 1.064 mum in a two-beam configuration is also examined.

Ischemic postconditioning and subanesthetic S(+)-Ketamine infusion: effects on renal function and histology in rats

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)