Phonon spectra of clean and Ni-terminated diamond (111) surfaces: An ab-initio study

The phonon densities of states (ph-DOSs) of clean and Ni-terminated C(111) surfaces with 1 × 1 and 2 × 1 surface structures were investigated using ab-initio density functional perturbation theory. The ph-DOSs showed vibrational spectra associated with the surface structures of C(111) and Ni/C(111). Further analyses of various surface phonon modes were performed to identify vibrational features involving the surface atoms of C(111) and Ni/C(111). These features provide important information for experimentally verifying the formation of a diamond bulk-like structure at Ni/C(111), as suggested in a previous study.     

The IR spectra of Mg5C(CO) complexes on the (0 0 1) surfaces of polycrystalline and single crystal MgO

The FTIR spectroscopy of carbon monoxide adsorbed on polycrystalline MgO smoke has been investigated as a function of the CO equilibrium pressure at constant temperature (60 K) (optical isotherm) and of the temperature (in the 300–60 K range) at constant CO pressure (optical isobar). In both cases the spectra fully reproduce those of CO adsorbed on the (0 0 1) surface of UHV cleaved single crystals [Heidberg et al., Surf. Sci. 331–333 (1995) 1467]. This result, never attained in previous investigations on dispersed MgO, contribute to bridging the gap which is commonly supposed to exist between surface science and the study of “real” (defective) systems. Depending on the surface coverage θ the main spectral features due to the CO/MgO smoke interaction are a single band shifting from 2157.5 (at θ→0) to 2150.2 cm⁻¹ (at θ=1/4) or a triplet, at 2151.5, 2137.2 and 2132.4 cm⁻¹ (at θ>1/4). These manifestations are due to the ν(CO) modes of Mg_5C²⁺· · · CO adducts formed on the (0 0 1) terminations of the cubic MgO smoke microcrystals. The formation of the CO monolayer is occurring in two different phases: (i) a first phase with CO oscillators perpendicularly oriented to the surface (2157–2150 cm⁻¹) and (ii) a second phase constituted by an array of coexisting perpendicular and tilted species (triplet at 2151.5, 2137.2 and 2132.4 cm⁻¹). A much weaker feature at 2167.5–2164 cm⁻¹ is assigned to Mg_4C²⁺· · · CO adducts at the edges of the microcrystals. The heat of adsorption of the perpendicular Mg_5C²⁺· · · CO complex in the first phase has been estimated from the optical isobar and results to be 11 kJ mol⁻¹.     

Deterioration of a polyurethane coating studied by positron annihilation spectroscopy: Correlation with surface properties

Deterioration of a polyurethane coating by Florida natural environments as a function of time up to 16 weeks was studied by positron annihilation spectroscopy. Doppler broadening energy spectroscopy (DBES) of annihilation irradiation and positron annihilation lifetime (PAL) were measured as a function of incident positron energy (0–30 keV). A significant decrease in the S‐defect parameter from DBES and the intensity of orthopositronium from PAL was observed as a function of weathering time. This is interpreted as a loss of free volume and holes as a result of the weathering process. The gloss and surface morphology in the same system were measured by glossimetry and atomic force microscopy (AFM), respectively. The gloss decreased and surface roughness increased as a function of weathering time. The AFM images showed a new feature of a spherically coagulated microstructure on the surface after weathering. Direct correlations between the decrease in gloss and the increase in roughness as well as the decrease in the S‐defect parameter from the DBES data and in the free volume from the PAL data were observed. These results were used to discuss the weathering process in terms of chemical and physical changes as a result of photodegradation in protective polymeric systems. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2290–2301, 2001     

Wetting and dewetting behaviour of hygroscopic liquids: Recent advancements

This review covers the most recent researches on wetting and dewetting phenomena related to the application of hygroscopic liquids in industry and technologies. Hygroscopic liquids actively absorb moisture from the surrounding air; therefore, they are used in the processes required for the moisturizing of surfaces or preventing the icing as well as control of evaporation rate and the humidity. The air humidity and wettability of substrates were shown to be crucial parameters affecting the wetting/dewetting kinetics of hygroscopic liquids. It is the adsorption of moisture on the hydrophilic surface that promotes the formation and spread of the precursor layer. The latter, in turn, is the droplet-spreading driver. The absorption of moisture by the liquid itself gives only a slight effect on wetting. The work devoted to the dewetting of hygroscopic liquids during evaporation, and the influence of thermal effects arising from contact with moist air on the wetting kinetics is also considered.     

Topologically minimal surfaces versus self-amalgamated Heegaard surfaces

Let V ∪SW be a Heegaard splitting of M,such that αM = α-W = F1 ∪ F2 and g(S) = 2g(F1)= 2g(F2). Let V * ∪S*W * be the self-amalgamation of V ∪SW. We show if d(S) 3 then S* is not a topologically minimal surface.     

Localisation and quantification of potential binding sites for compatibilisers on soft‐ and hardwood in wood–plastic composite systems

Chemical force microscopy (CFM) was used to characterise the surface of pine and beefwood with atomic force microscopy (AFM) tips coated with different compatibilisers. With the resulting force images, potential binding sites for compatibilisers, used in wood–plastic composites (WPC) to enhance adhesion between two relatively incompatible phases, were localised and quantified. Tips were coated with two commercially available polymers namely ethylene vinyl alcohol (EVOH) and polyethylene‐grafted maleic anhydride (PE‐g‐MA). It could be observed that the interaction forces between the EVOH coated tip and the wood surface was highly species sensitive, whereas adhesive forces measured between the PE‐g‐MA coated tip and the wood surface were comparable for both wood species. The force maps show that wood species differ in the distribution of functional groups, and the force histograms show that the frequency distribution of the adhesive forces varied for the two wood species. The adhesive force maps clearly show a difference between wood/compatibiliser systems, and the differences can be related to the chemical composition of the wood species. The results confirm that not all compatibilisers are equally suitable for all wood species and these results were confirmed by mechanical tensile tests of WPC systems in a related study. Copyright © 2016 John Wiley & Sons, Ltd.     

A theoretical study of the mechanism and kinetics of F+N3 reactions.

Both the singlet(1A') and triplet(3A') potential energy surfaces (PESs) of F+N(3) reactions are investigated using the complete-active-space self-consistent field (CASSCF) and the multireference configuration interaction (MRCI) methods with a proper active space. The minimum energy crossing point (MECP) at the intersection seam between the 1A' and 3A' PESs is located and used to clarify the reaction mechanisms. Two triplet transition states are found, with one in the cis form and the other one in the trans form. Further kinetic calculations are performed with the canonical unified statistical (CUS) theory on the singlet PES and the improved canonical variational transition-state (ICVT) method on the triplet PES. The rate constants are also reported. At 298 K, the calculated rate constant is in reasonably good agreement with experimental values, and spin-orbit coupling effects lower it by 28 %. The spectroscopic constants derived from the fitted potential-energy curves for the singlet and triplet states of NF are in very good agreement with experimental values. Our calculations indicate that the adiabatic reaction on the singlet PES leading to NF(a(1)Delta)+N(2) is the major channel, whereas the nonadiabatic reaction through the MECP, which leads to NF(X(3)Sigma(-))+N(2), is a minor channel.     

表面张力对疏水微结构表面减阻的影响

通过构造具有棋盘状微结构的疏水表面,考虑表面张力的影响,利用定常与非定常结合的数值模拟方法,研究了疏水表面在湍流状态下的减阻特性以及微结构内气体封存的效果,其中Re=3000—30000.在低雷诺数下,疏水表面微结构内气体封存状态良好,减阻率最高约为30%;随着雷诺数的增大,压差阻力增大,减阻率有下降趋势.当来流速度过大时,水会大量进入微结构,疏水表面的减阻率变化剧烈,且已经不再减阻.结果表明,表面张力削弱了壁面切应力的影响,使得低雷诺数下微结构内气体能够有效封存,进而减小壁面阻力.     

BayesWHAM: A Bayesian approach for free energy estimation,reweighting, and uncertainty quantification in the weighted histogram analysis method

The weighted histogram analysis method (WHAM) is a powerful approach to estimate molecular free energy surfaces (FES) from biased simulation data. Bayesian reformulations of WHAM are valuable in proving statistically optimal use of the data and providing a transparent means to incorporate regularizing priors and estimate statistical uncertainties. In this work, we develop a fully Bayesian treatment of WHAM to generate statistically optimal FES estimates in any number of biasing dimensions under arbitrary choices of the Bayes prior. Rigorous uncertainty estimates are generated by Metropolis‐Hastings sampling from the Bayes posterior. We also report a means to project the FES and its uncertainties into arbitrary auxiliary order parameters beyond those in which biased sampling was conducted. We demonstrate the approaches in applications of alanine dipeptide and the unthreading of a synthetic mimic of the astexin‐3 lasso peptide. Open‐source MATLAB and Python implementations of our codes are available for free public download. © 2017 Wiley Periodicals, Inc.