Deviation from equilibrium conditions in molecular dynamic simulations of homogeneous nucleation

We present a comparison between Monte Carlo (MC) results for homogeneous vapourliquid nucleation of Lennard-Jones clusters and previously published values from molecular dynamics (MD) simulations. Both the MC and MD methods sample real cluster configuration distributions. In the MD simulations the extent of the temperature fluctuation is usually controlled with an artificial thermostat rather than with more realistic carrier gas. In this study primarily velocity scaling thermostat is considered, but also Nos´e-Hoover, Berendsen and stochastic Langevin thermostat methods are covered. The nucleation rates based on a kinetic scheme and the canonical MC calculation serve as a point of reference since they by definition describe an equilibrated system. The studied temperature range is from T = 0.3 to 0.65 ϵ/k. The kinetic scheme reproduces well the isothermal nucleation rates obtained by Wedekind et al. [J. Chem. Phys. 127, 064501 (2007)] using MD simulations with carrier gas. The nucleation rates obtained by artificially thermostatted MD simulations are consistently lower than the reference nucleation rates based on MC calculations. The discrepancy increases up to several orders of magnitude when the density of the nucleating vapour decreases. At low temperatures the difference to the MC-based reference nucleation rates in some cases exceeds the maximal nonisothermal effect predicted by classical theory of Feder et al. [Adv. Phys. 15, 111 (1966)].Peer reviewe

Nucleation in the Ising ferromagnet by a field spatially spreading in time

The nucleation in Ising ferromagnet has been studied by Monte Carlo simulation. Here, the magnetic field is spreading over the space in time. The nucleation time is observed to increase as compared to that in the case of static field. The clusters of negative spins is observed to grow from the center. The growth of effective magnetisation is studied with temperature and the strength of spreading magnetic field. The ratio of nucleation time and effective time is also studied with strength of spreading magnetic field. The effective time would introduce itself as a new scale of time in the case of nucleation by spatially spreading magnetic field. The effective time and the nucleation time both are observed to decrease as a power law fashion with the rate factor of spreading magnetic field.Comment: 16 pages Latex, 8 figures, To appear in Physica

Reaction Mechanisms Underlying Unfunctionalized Alkyl Nitrate Hydrolysis in Aqueous Aerosols

Alkyl nitrates (ANs) are both sinks and sources of nitrogen oxide radicals (NOx = NO + NO2) in the atmosphere. Their reactions affect both the nitrogen cycle and ozone formation and therefore air quality and climate. ANs can be emitted to the atmosphere or produced in the gas phase. In either case, they can partition into aqueous aerosols, where they might undergo hydrolysis, producing highly soluble nitrate products, and act as a permanent sink for NOx. The kinetics of AN hydrolysis partly determines the extent of AN contribution to the nitrogen cycle. However, kinetics of many ANs in various aerosols is unknown, and there are conflicting arguments about the effect of acidity and basicity on the hydrolysis process. Using computational methods, this study proposes a mechanism for the reactions of methyl, ethyl, propyl, and butyl nitrates with OH- (hydroxyl ion; basic hydrolysis), water (neutral hydrolysis), and H3O+ (hydronium ion; acidic hydrolysis). Using quantum chemical data and transition state theory, we follow the effect of pH on the contribution of the basic, neutral, and acidic hydrolysis channels, and the rate coefficients of AN hydrolysis over a wide range of pH. Our results show that basic hydrolysis (i.e., AN reaction with OH-) is the most kinetically and thermodynamically favorable reaction among our evaluated reaction schemes. Furthermore, comparison of our kinetics results with experimental data suggests that there is an as yet unknown acidic mechanism responsible for acidic catalysis of AN hydrolysis.Peer reviewe

Non-LTE dust nucleation in sub-saturated vapors

We use the kinetic theory of nucleation to explore the properties of dust nucleation in sub-saturated vapors. Due to radiation losses, the sub-critical clusters have a smaller temperature compared to their vapor. This alters the dynamical balance between attachment and detachment of monomers, allowing for stable nucleation of grains in vapors that are sub-saturated for their temperature. We find this effect particularly important at low densities and in the absence of a strong background radiation field. We find new conditions for stable nucleation in the n-T phase diagram. The nucleation in the non-LTE regions is likely to be at much slower rate than in the super-saturated vapors. We evaluate the nucleation rate, warning the reader that it does depend on poorly substantiated properties of the macro-molecules assumed in the computation. On the other hand, the conditions for nucleation depend only on the properties of the large stable grains and are more robust. We finally point out that this mechanism may be relevant in the early universe as an initial dust pollution mechanism, since once the interstellar medium is polluted with dust, mantle growth is likely to be dominant over non-LTE nucleation in the diffuse medium.Comment: 8 pages, 8 figures, accepted for publication in MNRA

Exploring the chemical fate of the sulfate radical anion by reaction with sulfur dioxide in the gas phase

Peer reviewe

Charged and Neutral Binary Nucleation of Sulfuric Acid in Free Troposphere Conditions

We present a data set of binary nucleation of sulfuric acid and water, measured in the CLOUD chamber at CERN during the CLOUD3 and CLOUD5 campaigns. Four parameters have been varied to cover neutral and ion-induced binary nucleation processes: Sulfuric acid concentration (1e5 to 1e8 molecules per cm^(−3)), relative humidity (10% to 80%), temperature (208-293K) and ion concentration (0-4000 ions per cm^(−3)). In addition, classical nucleation theory implemented with hydrates and ion induced nucleation is compared with the data set. Our model and data are also compared with nucleation rates measured at Puy de Dome in the tropopause

Microcanonical Determination of the Interface Tension of Flat and Curved Interfaces from Monte Carlo Simulations

The investigation of phase coexistence in systems with multi-component order parameters in finite systems is discussed, and as a generic example, Monte Carlo simulations of the two-dimensional q-state Potts model (q=30) on LxL square lattices (40<=L<=100) are presented. It is shown that the microcanonical ensemble is well-suited both to find the precise location of the first order phase transition and to obtain an accurate estimate for the interfacial free energy between coexisting ordered and disordered phases. For this purpose, a microcanonical version of the heatbath algorithm is implemented. The finite size behaviour of the loop in the curve describing the inverse temperature versus energy density is discussed, emphasizing that the extrema do not have the meaning of van der Waals-like "spinodal points" separating metastable from unstable states, but rather describe the onset of heterophase states: droplet/bubble evaporation/condensation transitions. Thus all parts of these loops, including the parts that correspond to a negative specific heat, describe phase coexistence in full thermal equilibrium. However, the estimates for the curvature-dependent interface tension of the droplets and bubbles suffer from unexpected and unexplained large finite size effects which need further study.Comment: submitted to special issue "Liquid Matter" of Journal of Physics C: Condensed Matter on occasion of the 8th Liquid Matter Conference held Sept. 6-10, 2011 in Vienna, Austri

Clustering mechanism of oxocarboxylic acids involving hydration reaction : Implications for the atmospheric models

The formation of atmospheric aerosol particles from condensable gases is a dominant source of particulate matter in the boundary layer, but the mechanism is still ambiguous. During the clustering process, precursors with di↵erent reactivities can induce various chemical reactions in addition to the formation of hydrogen bonds. However, the clustering mechanism involving chemical reactions is rarely considered in most of the nucleation process models. Oxocarboxylic acids are common compositions of secondary organic aerosol, but the role of oxocarboxylic acids in secondary organic aerosol formation is still not fully understood. In this paper, glyoxylic acid, the simplest and the most abundant atmospheric oxocarboxylic acids, has been selected as a representative example of oxocarboxylic acids in order to study the clustering mechanism involving hydration reaction using Density Functional Theory combined with the Atmospheric Clusters Dynamic Code. The hydration reaction of glyoxylic acid can occur either in the gas phase or during the clustering process. In atmospheric conditions, the total conversion ratio of glyoxylic acid to its hydration reaction product (2,2-dihydroxyacetic acid) in both gas phase and clusters can be up to 85%, andthe product can further participate in the clustering process. The di↵erences in cluster structures and properties induced by the hydration reaction lead to significant di↵erences in cluster formation rates and pathways at relatively low temperatures.Peer reviewe

The charging of neutral dimethylamine and dimethylamine-sulfuric acid clusters using protonated acetone

Sulfuric acid is generally considered one of the most important substances taking part in atmospheric particle formation. However, in typical atmospheric conditions in the lower troposphere, sulfuric acid and water alone are unable to form particles. It has been suggested that strong bases may stabilize sulfuric acid clusters so that particle formation may occur. More to the point, amines - strong organic bases - have become the subject of interest as possible cause for such stabilization. To probe whether amines play a role in atmospheric nucleation, we need to be able to measure accurately the gas-phase amine vapour concentration. Such measurements often include charging the neutral molecules and molecular clusters in the sample. Since amines are bases, the charging process should introduce a positive charge. This can be achieved by, for example, using chemical ionization with a positively charged reagent with a suitable proton affinity. In our study, we have used quantum chemical methods combined with a cluster dynamics code to study the use of acetone as a reagent ion in chemical ionization and compared the results with measurements performed with a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer (CI-APi-TOF). The computational results indicate that protonated acetone is an effective reagent in chemical ionization. However, in the experiments the reagent ions were not depleted at the predicted dimethylamine concentrations, indicating that either the modelling scheme or the experimental results - or both - contain unidentified sources of error.Peer reviewe

Effect of ions on sulfuric acid-water binary particle formation : 2. Experimental data and comparison with QC-normalized classical nucleation theory

We report comprehensive, demonstrably contaminant-free measurements of binary particle formation rates by sulfuric acid and water for neutral and ion-induced pathways conducted in the European Organization for Nuclear Research Cosmics Leaving Outdoor Droplets chamber. The recently developed Atmospheric Pressure interface-time of flight-mass spectrometer was used to detect contaminants in charged clusters and to identify runs free of any contaminants. Four parameters were varied to cover ambient conditions: sulfuric acid concentration (10(5) to 10(9)molcm(-3)), relative humidity (11% to 58%), temperature (207K to 299K), and total ion concentration (0 to 6800ionscm(-3)). Formation rates were directly measured with novel instruments at sizes close to the critical cluster size (mobility size of 1.3nm to 3.2nm). We compare our results with predictions from Classical Nucleation Theory normalized by Quantum Chemical calculation (QC-normalized CNT), which is described in a companion paper. The formation rates predicted by the QC-normalized CNT were extended from critical cluster sizes to measured sizes using the UHMA2 sectional particle microphysics model. Our results show, for the first time, good agreement between predicted and measured particle formation rates for the binary (neutral and ion-induced) sulfuric acid-water system. Formation rates increase with RH, sulfuric acid, and ion concentrations and decrease with temperature at fixed RH and sulfuric acid concentration. Under atmospheric conditions, neutral particle formation dominates at low temperatures, while ion-induced particle formation dominates at higher temperatures. The good agreement between the theory and our comprehensive data set gives confidence in using the QC-normalized CNT as a powerful tool to study neutral and ion-induced binary particle formation in atmospheric modeling.Peer reviewe