Impurity-stimulated heterogeneous nucleation of supercooled H2 clusters

The sizes and mass spectra of large (N=1900-13,700 molecules) cold (approximately 3.1 K) H2 clusters have been measured after scattering from CO molecules. Cluster-size measurements after between 2 and 8 collisions indicate that 7% of the H2 molecules are evaporated. This loss agrees with calculations for the number of H2 molecules evaporated by the heat released in the transition from an initial liquid state to a final solid state. Even though heterogeneous nucleation is initiated after only a few collisions with CO molecules, the mass spectra show that additional captured CO molecules coagulate to form large CO clusters with up to n=11 molecules, suggesting that the outer layer is sufficiently liquidlike to facilitate mobility of the CO molecules. Since the calculated H2 cluster temperature (approximately 3.1 K) is below the superfluid transition temperature predicted for pH2 with density between 40% and 80% of the triple-point density, a shell-like region of low density near the cluster surface can be expected to be superfluid.     

First-principles studies on the reactions of O2 with silicon clusters

The reactions of an O(2) molecule with the neutral and positively charged Si(n)(n = 3-16) clusters are studied with first-principles calculations. Neutral Si(n)(n = 4,5,6,7,10,14) and charged Si(n) (+)(n = 4,5,6,7,13,15) clusters show higher inertness to O(2) molecule adsorption, which is in good agreement with experimental results. Both charge transfer and hybridizations between Si and O play an important role in the dissociative adsorption of O(2) molecule. We find that the spin triplet-single conversion of O(2) molecule is always accompanied with O(2) dissociatively chemisorbed on the Si(n) clusters.     

Homogeneous nucleation at high supersaturation and heterogeneous nucleation on microscopic wettable particles: A hybrid thermodynamic/density-functional theory

Homogeneous nucleation at high supersaturation of vapor and heterogeneous nucleation on microscopic wettable particles are studied on the basis of Lennard-Jones model system. A hybrid classical thermodynamics and density-functional theory (DFT) approach is undertaken to treat the nucleation problems. Local-density approximation and weighted-density approximation are employed within the framework of DFT. Special attention is given to the disjoining pressure of small liquid droplets, which is dependent on the thickness of wetting film and radius of the wettable particle. Different contributions to the disjoining pressure are examined using both analytical estimations and numerical DFT calculation. It is shown that van der Waals interaction results in negative contribution to the disjoining pressure. The presence of wettable particles results in positive contribution to the disjoining pressure, which plays the key role in the heterogeneous nucleation. Several definitions of the surface tension of liquid droplets are discussed. Curvature dependence of the surface tension of small liquid droplets is computed. The important characteristics of nucleation, including the formation free energy of the droplet and nucleation barrier height, are obtained.     

Kinetics of heterogeneous reactions of HO2 radical at ambient concentration levels with (NH4)2SO4 and NaCl aerosol particles

The HO2 uptake coefficient (gamma) for inorganic submicrometer wet and dry aerosol particles ((NH4)2SO4 and NaCl) under ambient conditions (760 Torr and 296 +/- 2 K) was measured using an aerosol flow tube (AFT) coupled with a chemical conversion/laser-induced fluorescence (CC/LIF) technique. The CC/LIF technique enabled experiments to be performed at almost the same HO2 radical concentration as that in the atmosphere. HO2 radicals were injected into the AFT through a vertically movable Pyrex tube. Injector position-dependent profiles of LIF intensity were measured as a function of aerosol concentration. Measured gamma values for dry aerosols of (NH4)2SO4 were 0.04 +/- 0.02 and 0.05 +/- 0.02 at 20% and 45% relative humidity (RH), respectively, while those of NaCl were <0.01 and 0.02 +/- 0.01 at 20% and 53% RH, respectively. For wet (NH4)2SO4 aerosols, measured gamma values were 0.11 +/- 0.03, 0.15 +/- 0.03, 0.17 +/- 0.04, and 0.19 +/- 0.04, at 45%, 55%, 65%, and 75% RH, respectively, whereas for wet NaCl aerosols the values were 0.11 +/- 0.03, 0.09 +/- 0.02, and 0.10 +/- 0.02 for 53%, 63%, and 75% RH, respectively. Wet (NH4)2SO4 and NaCl aerosols doped with CuSO4 showed gamma values of 0.53 +/- 0.12 and 0.65 +/- 0.17, respectively. These results suggest that compositions, RH, and phase for aerosol particles are significant to HO2 uptake. Potential HO2 loss processes and their atmospheric contributions are discussed.     

Sequential ene, Diels-Alder reactions of AF4-yne with 1,3,5-cycloheptatriene

(4,5-Dehydro)-1,1,2,2,9,9,10,10-octafluoro [2.2]paracyclophane (AF4-yne) undergoes an ene reaction with 1,3,5-cycloheptatriene, the adduct of which subsequently undergoes a further Diels-Alder reaction with a second equivalent of AF4-yne to give two stereoisomeric 2:1 adducts. A very small amount of the classic 1:1 Diels-Alder adduct also can be isolated from the reaction. Structure assignments of all products were determined by NMR through a series of H1-H1, H1-C13 one bond, and H1-C13 two and three bond correlation experiments as well as H1-H1 NOE experiments.     

The effect of clusters and heterogeneous reactions on non-equilibrium plasma flue gas cleaning

Theoretical investigation of the effect of molecular clusters and aerosol particles on non-equilibrium plasma flue gas cleaning was made in this paper. Two types of heterogeneous reactions in aerosol and clusters are considered. It was shown that in both cases these reactions are essential in the evaluation of chemical composition. As a result of theoretical approach and modelling, the optimum regime of plasma generation for essential decreasing of purification energy cost was established.     

A kinetic approach to the theory of heterogeneous nucleation on soluble particles during the deliquescence stage

Deliquescence is the dissolution of a solid nucleus in a liquid film formed on the nucleus due to vapor condensation. Previously, the kinetics of deliquescence was examined in the framework of the capillarity approximation which involves the thermodynamic interfacial tensions for a thin film and the approximation of uniform density therein. In the present paper we propose a kinetic approach to the theory of deliquescence which avoids the use of the above macroscopic quantities for thin films. The rates of emission of molecules from the liquid film into the vapor and from the solid core into the liquid film are determined through a first passage time analysis whereas the respective rates of absorption are calculated through the gas kinetic theory. The first passage time is obtained by solving the single-molecule master equation for the probability distribution of a "surface" molecule moving in a potential field created by the cluster. Furthermore, the time evolution of the liquid film around the solid core is described by means of two mass balance equations which involve the rates of absorption and emission of molecules by the film at its two interfaces. When the deliquescence of an ensemble of solid particles occurs by means of large fluctuations, the time evolution of the distribution of composite droplets (liquid film+solid core) with respect to the independent variables of state is governed by a Fokker-Planck kinetic equation. When both the vapor and the solid soluble particles are single component, this equation has the form of the kinetic equation of binary nucleation. A steady-state solution for this equation is obtained by the method of separation of variables. The theory is illustrated with numerical calculation regarding the deliquescence of spherical particles in a water vapor with intermolecular interactions of the Lennard-Jones kind. The new approach allows one to qualitatively explain an important feature of experimental data on deliquescence, namely the occurrence of nonsharp deliquescence, a feature that the previous deliquescence theory based on classical thermodynamics could not account for.     

Oxidative reactions of silicon atoms and clusters at ultralow temperature in helium droplets

The reaction between Si and O(2) was studied in liquid He droplets at low temperature (T = 0.37 K) by monitoring the energy release during the reaction. Additionally, the reactions of Si atoms and clusters with the oxidation agents H(2)O and O(2) have been studied by mass spectrometry. It was found that Si atoms react fast with O(2) molecules. On the other hand, Si atoms and clusters do not react with H(2)O molecules. The energy released during the chemical reaction leads to the ejection of the products from small He droplets. In contrast, large He droplets (N(He) > 20000) are capable of keeping part of the reaction products in their interior. The observation of SiO(2) products with the mass spectrometer reveals that the He droplet can stabilize intermediate products in the exit channel.     

Formation of endogenous MgO and MgAl2O4 particles and their possibility of acting as substrate for heterogeneous nucleation of aluminum grains

Aluminum containing 4 wt.% magnesium was oxidized at a temperature for different oxidation times and analyzed by high‐resolution electron microscopy. A thin oxidized layer of about 5 µm, which is composed of MgO, forms at short oxidation time and gradually increases. High‐resolution microstructures reveal that the oxidized layers are porous regardless of oxidation time. After extended oxidation time, discrete MgAl₂O₄ particles formed as a result of the reaction of initially formed MgO, liquid aluminum, and oxygen introduced from air through the porous MgO. Furthermore, it is clear by high‐resolution lattice images that MgAl₂O₄ particles are covered with thin Al₂O₃, whereas MgO is bonded intimately to aluminum. Therefore, MgAl₂O₄ particles that form naturally during oxidation are difficult to act as a direct substrate for nucleation of aluminum grains because of the coverage of Al₂O₃. In contrast, MgO shows the possibility of acting as a substrate for the aluminum nucleation. The formation mechanism of MgO and MgAl₂O₄ and their possibility of acting as substrates for nucleation of aluminum grains suggest that atomic level bonding and mismatches of nucleant/nucleus metal should be considered for correct evaluation of the possibility of heterogeneous nucleation of metallic matrix on a potent nucleant. © 2015 The Authors. Surface and Interface Analysis Published by John Wiley & Sons, Ltd.     

In situ scanning tunneling microscopy of oxide-supported metal clusters: nucleation,growth, and thermal evolution of individual particles

An experimental approach was developed for imaging the nucleation and growth of individual oxide-supported nanoparticles and their subsequent in situ chemical and thermal treatments by scanning tunneling microscopy (STM). The potential of the method is demonstrated for Au nanoparticles supported on a reduced TiO(2) substrate where a cluster-by-cluster comparison is made of the morphological evolution and stability of nanoparticles during their nucleation and thermal annealing. Using this methodology the details of the nucleation and growth kinetics can be directly observed.     

Large silicon clusters: Confirmation of Phillips'' conjecture

This paper attempts to verify the hypothesis put forward by Phillips that large silicon clusters are arranged in a cylindrical shape, as stacked quasigraphitic rings. It is shown that the periodic variations in reactivity can probably be explained by this hypothesis. A tight-binding calculation is employed, and the geometry and charge distribution of clusters ranging in size from 30 to 45 atoms is explored.     

Tetranuclear osmium clusters from the reactions of H4 Os4 (CO)12 with alkenes

Organotetraosmium cluster compounds of the general formulae H₃ Os₄ (CO)₁₁HC₂HR and H₂ Os₄ (CO)₁₁HC₂ R (where R = H, Ph or t-Bu) have been prepared from reactions of H₄ Os₄ (CO)₁₂. with the appropriate alkene.     

Size-dependent reactions of ammonium bisulfate clusters with dimethylamine

The reaction kinetics of ammonium bisulfate clusters with dimethylamine (DMA) gas were investigated using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Clusters ranged in size from 1 to 10 bisulfate ions. Although displacement of the first several ammonium ions by DMA occurred with near unit efficiency, displacement of the final ammonium ion was cluster size dependent. For small clusters, all ammonium ions are exposed to incoming DMA molecules, allowing for facile exchange ("surface" exchange). However, with increasing cluster size, an ammonium ion can be trapped in an inaccessible region of the cluster ("core" exchange), thereby rendering exchange difficult. DMA was also observed to add onto existing dimethylaminium bisulfate clusters above a critical size, whereas ammonia did not add onto ammonium bisulfate clusters. The results suggest that as the cluster size increases, di-dimethylaminium sulfate formation becomes more favorable. The results of this study give further evidence to suggest that ambient sub-3 nm diameter particles are likely to contain aminium salts rather than ammonium salts.     

Evolution of heterogeneous catalytic reactions kinetics with time

An overview of development of heterogeneous catalytic kinetic concepts is presented. An emphasis is made on the application of mechanistically sound models, which are needed as a part of the understanding of catalytic reactions on a molecular level as well as of the design and the intensification of chemical processes. Such models should include among other parameters the size and geometry of reacting molecules, size of nanoclusters and deactivation as a part of the reaction mechanism.     

Connecting theory with experiment to understand the initial nucleation steps of heteropolyoxometalate clusters

A complimentary combination of Density Functional Theory (DFT) methodology and Electrospray Ionization-Mass Spectrometry (ESI-MS) has been utilized to increase our limited understanding of the first nucleation steps in the formation of the [XM(12)O(40)](n-) Keggin polyoxometalates (POMs) (where addenda metal atom M = W or Mo, and the heteroatom X = P or As). We postulate that the first key steps of nucleation into discrete, high nuclearity heteropolyanions proceed via the formation of isodinuclear species (e.g. [M(2)O(7)](2-)), which undergo successive steps of protonation and water condensation to form a heterotrinuclear fragment, which acts as a template for the constituent parts required for subsequent aggregation and formation of the plenary Keggin heteropolyanion. The stability of calculated structures of the numerous postulated intermediates has been analysed and discussed in detail, and these results complemented using experimental mass spectrometry, using an assembly (reaction solution analysis) and disassembly (fragmentation of single crystals) approach. Overall, no significant differences between the Keggin POMs were found when changing the addenda metal atom (W or Mo) or the heteroatom (P or As); although small differences among the lowest-energy structures were detected.     

Molecular dynamics implementation in MSINDO: study of silicon clusters

Born-Oppenheimer molecular dynamics is implemented in the semiempirical self-consistent field molecular orbital method MSINDO. The method is employed for the investigation of the structure and dynamics of silicon clusters of various sizes. The reliability of the present parameterization for silicon compounds is demonstrated by a comparison of the results of simulated annealing and of density functional calculations of Si(n) clusters (n = 5-7). The melting behavior of the Si(7) cluster is investigated and the MSINDO results are compared to previous high-level calculations. The efficiency of the present approach for the treatment of large systems is demonstrated by an extensive simulated annealing study of the Si(45) and Si(60) clusters. New Si(45) and Si(60) structures are found and evaluated. The relative stability of various energy minimum structures is compared with density functional calculations and available literature data.     

Diffusion-influenced reactions of particles with several active sites

The main concern of the present work is consideration of sterically specific liquid-phase reactions in the case where one of the reactants has several active sites. In kinematic approximation we derived compact formulas for partial rate constants of individual active sites. Reaction rates are expressed via the kinetic rate constants and convolutions of the free Green functions over reaction zones. These results are valid for arbitrary geometry of reactants and active sites. Effects of mutual influence of the active sites were studied, their simple estimate was proposed.     

Heterogeneous reactions of sulfur dioxide with carbonaceous particles

The rate of adsorption of SO₂ on a prototype carbonaceous surface was measured at low pressure in a flow reactor. The measured rate indicates a maximum atmospheric loss of SO₂ by heterogeneous reaction of 1%/h for a particle density of 100 μg/m³. The capacity of carbon particles to adsorb SO₂ is limited at ～1 mg SO₂ g^?1 C. NO₂ has no effect on the rate of SO₂ adsorption or the saturation behavior.