Models for thermal dissociation of silane on a polysilicon surface

Simple models for the thermally activated dissociation reaction of silane and silicon growth on a polycrystalline silicon surface are presented. The models are fitted to recent experimental molecular beam scattering data for the low-pressure reactive sticking coefficient. Thermally activated few-step models fit the data reasonably well, and thus, we are able to explain the temperature and pressure dependencies of the observed deposition rate.     

Fluctuating lattice-Boltzmann model for complex fluids

We develop and test numerically a lattice-Boltzmann (LB) model for nonideal fluids that incorporates thermal fluctuations. The fluid model is a momentum-conserving thermostat, for which we demonstrate how the temperature can be made equal at all length scales present in the system by having noise both locally in the stress tensor and by shaking the whole system in accord with the local temperature. The validity of the model is extended to a broad range of sound velocities. Our model features a consistent coupling scheme between the fluid and solid molecular dynamics objects, allowing us to use the LB fluid as a heat bath for solutes evolving in time without external Langevin noise added to the solute. This property expands the applicability of LB models to dense, strongly correlated systems with thermal fluctuations and potentially nonideal equations of state. Tests on the fluid itself and on static and dynamic properties of a coarse-grained polymer chain under strong hydrodynamic interactions are used to benchmark the model. The model produces results for single-chain diffusion that are in quantitative agreement with theory.     

Hydrophobicity within the three-dimensional Mercedes-Benz model: potential of mean force

We use the three-dimensional Mercedes-Benz model for water and Monte Carlo simulations to study the structure and thermodynamics of the hydrophobic interaction. Radial distribution functions are used to classify different cases of the interaction, namely, contact configurations, solvent separated configurations, and desolvation configurations. The temperature dependence of these cases is shown to be in qualitative agreement with atomistic models of water. In particular, while the energy for the formation of contact configurations is favored by entropy, its strengthening with increasing temperature is accounted for by enthalpy. This is consistent with our simulated heat capacity. An important feature of the model is that it can be used to account for well-converged thermodynamics quantities, e.g., the heat capacity of transfer. Microscopic mechanisms for the temperature dependence of the hydrophobic interaction are discussed at the molecular level based on the conceptual simplicity of the model.     

HXeOBr in a xenon matrix

We report on a new noble-gas molecule HXeOBr prepared in a low-temperature xenon matrix from the HBr and N(2)O precursors by UV photolysis and thermal annealing. This molecule is assigned with the help of deuteration experiments and ab initio calculations including anharmonic methods. The H-Xe stretching frequency of HXeOBr is observed at 1634 cm(-1), which is larger by 56 cm(-1) than the frequency of HXeOH identified previously. The experiments show a higher thermal stability of HXeOBr molecules in a xenon matrix compared to HXeOH.     

Feasibility of a liquid-phase microextraction sample clean-up and liquid chromatographic/mass spectrometric screening method for selected anabolic steroid glucuronides in biological samples

Anabolic androgenic steroids (AAS) are metabolized extensively in the human body, resulting mainly in the formation of glucuronide conjugates. Current detection methods for AAS are based on gas chromatographic/mass spectrometric (GC/MS) analysis of the hydrolyzed steroid aglycones. These analyses require laborious sample preparation steps and are therefore time consuming. Our interest was to develop a rapid and straightforward method for intact steroid glucuronides in biological samples, using liquid-phase microextraction (LPME) sample clean-up and concentration method combined with liquid chromatographic/tandem mass spectrometric (LC/MS/MS) analysis. The applicability of LPME was optimized for 13 steroid glucuronides, and compared with conventional liquid-liquid extraction (LLE) and solid-phase extraction (SPE) procedures. An LC/MS/MS method was developed for the quantitative detection of AAS glucuronides, using a deuterium-labeled steroid glucuronide as the internal standard. LPME, owing to its high specificity, was shown to be better suited than conventional LLE and SPE for the clean-up of urinary AAS glucuronides. The LPME/LC/MS/MS method was fast and reliable, offering acceptable reproducibility and linearity with detection limits in the range 2-20 ng ml(-1) for most of the selected AAS glucuronides. The method was successfully applied to in vitro metabolic studies, and also tested with an authentic forensic urine sample. For a urine matrix the method still has some unsolved problems with specificity, which should be overcome before the method can be reliably used for doping analysis, but still offering additional and complementary data for current GC/MS analyses.     

Nucleation, Growth, and Scaling in Slow Combustion

We study the nucleation and growth of flame fronts in slow combustion. This is modeled by a set of reaction-diffusion equations for the temperature field, coupled to a background of reactants and augmented by a term describing random temperature fluctuations for ignition. We establish connections between this model and the classical theories of nucleation and growth of droplets from a metastable phase. Our results are in good agreement with theoretical predictions.     

Packing dimension and Ahlfors regularity of porous sets in metric spaces

Let X be a metric measure space with an s-regular measure μ. We prove that if A ì X{A\subset X} is r{\varrho} -porous, then dim_p(A) ￡ s-cr^s{{\rm {dim}_p}(A)\le s-c\varrho^s} where dim_p is the packing dimension and c is a positive constant which depends on s and the structure constants of μ. This is an analogue of a well known asymptotically sharp result in Euclidean spaces. We illustrate by an example that the corresponding result is not valid if μ is a doubling measure. However, in the doubling case we find a fixed N ì X{N\subset X} with μ(N) = 0 such that dim_p(A) ￡ dim_p(X)-c(log\tfrac1r)^-1r^t{{\rm {dim}_p}(A)\le{\rm {dim}_p}(X)-c(\log \tfrac1\varrho)^{-1}\varrho^t} for all r{\varrho} -porous sets A ì X\ N{A \subset X{\setminus} N} . Here c and t are constants which depend on the structure constant of μ. Finally, we characterize uniformly porous sets in complete s-regular metric spaces in terms of regular sets by verifying that A is uniformly porous if and only if there is t < s and a t-regular set F such that A ì F{A\subset F} .     

Multiscale modeling of submonolayer growth for Fe/Mo (110)

We use a multiscale approach to study a lattice-gas model of submonolayer growth of Fe/Mo (110) by Molecular Beam Epitaxy. To begin with, we construct a two-dimensional lattice-gas model of the Fe/Mo (110) system based on our first-principles calculations of the monomer diffusion barrier and adatom-adatom interactions. The model is investigated by equilibrium Monte Carlo (MC) simulations to compute the diffusion coefficients of Fe islands of different sizes. These diffusion coefficients are used as input to the coarse-grained kinetic rate equation (KRE) approach. We also evaluate effects of the range of Fe-Fe interaction, restriction of interaction to third nearest neighbors allowed to develop feasible atomistic kinetic Monte Carlo (KMC) model. We calculate time evolution of the island size distributions by both KMC and KRE methods and find good agreement between the two methods.     

Principles and calibration of collinear photofragmentation and atomic absorption spectroscopy

The kinetics of signal formation in collinear photofragmentation and atomic absorption spectroscopy (CPFAAS) are discussed, and theoretical equations describing the relation between the concentration of the target molecule and the detected atomic absorption in case of pure and impure samples are derived. The validity of the equation for pure samples is studied experimentally by comparing measured target molecule concentrations to concentrations determined using two other independent techniques. Our study shows that CPFAAS is capable of measuring target molecule concentrations from parts per billion (ppb) to hundreds of parts per million (ppm) in microsecond timescale. Moreover, the possibility to extend the dynamic range to cover eight orders of magnitude with a proper selection of fragmentation light source is discussed. The maximum deviation between the CPFAAS technique and a reference measurement technique is found to be less than 5 %. In this study, potassium chloride vapor and atomic potassium are used as a target molecule and a probed atom, respectively.