Warm Cores around Regions of Low-Mass Star Formation

Warm cores (or hot corinos) around low-mass protostellar objects show a rich chemistry with strong spatial variations. This chemistry is generally attributed to the sublimation of icy mantles on dust grains initiated by the warming effect of the stellar radiation. We have used a model of the chemistry in warm cores in which the sublimation process is based on extensive laboratory data; these data indicate that sublimation from mixed ices occurs in several well-defined temperature bands. We have determined the position of these bands for the slow warming by a solar-mass star. The resulting chemistry is dominated by the sublimation process and by subsequent gas-phase reactions; strong spatial and temporal variations in certain molecular species are found to occur, and our results are, in general, consistent with observational results for the well-studied source IRAS 16293-2422. The model used is similar to one that describes the chemistry of hot cores. We infer that the chemistry of both hot cores and warm cores may be described by the same model (suitably adjusted for different physical parameters).Comment: 11 pages, 5 figures, 2 tables. Accepted by MNRA

General and physical chemistry

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Reactive molecular dynamics simulations of organometallic compound W(CO)6 fragmentation

Irradiation- and collision-induced fragmentation studies provide information about geometry, electronic properties and interactions between structural units of various molecular systems. Such knowledge brings insights into irradiation-driven chemistry of molecular systems which is exploited in different technological applications. An accurate atomistic-level simulation of irradiation-driven chemistry requires reliable models of molecular fragmentation which can be verified against mass spectrometry experiments. In this work fragmentation of a tungsten hexacarbonyl, W(CO)$_6$, molecule is studied by means of reactive molecular dynamics simulations. The quantitatively correct fragmentation picture including different fragmentation channels is reproduced. We show that distribution of the deposited energy over all degrees of freedom of the parent molecule leads to thermal evaporation of CO groups and the formation of W(CO)$_n^+$ ($n = 0-5$) fragments. Another type of fragments, WC(CO)$_n^+$ ($n = 0-4$), is produced due to cleavage of a C--O bond as a result of the localized energy deposition. Calculated fragment appearance energies are in good agreement with experimental data. These fragmentation mechanisms have a general physical nature and should take place in radiation-induced fragmentation of different molecular and biomolecular systems.Comment: 11 pages, 6 figures, submitted to European Physical Journal

Simplified half-life methods for the analysis of kinetic data

The analysis of reaction rate data has as its goal the determination of the order rate constant which characterize the data. Chemical reactions with one reactant and present simplified methods for accomplishing this goal are considered. The approaches presented involve the use of half lives or other fractional lives. These methods are particularly useful for the more elementary discussions of kinetics found in general and physical chemistry courses

Connecting local structure to interface formation: a molecular scale van der Waals theory of nonuniform liquids

This article reviews a new and general theory of nonuniform fluids that naturally incorporates molecular scale information into the classical van der Waals theory of slowly varying interfaces. The method optimally combines two standard approximations, molecular (mean) field theory to describe interface formation and linear response (or Gaussian fluctuation) theory to describe local structure. Accurate results have been found in many different applications in nonuniform simple fluids and these ideas may have important implications for the theory of hydrophobic interactions in water.Comment: 30 pages; 4 figures; to be published in Annual Reviews of Physical Chemistry, Vol. 5

Joint scalar PDF simulations of a bluff-body stabilised flame with the REDIM approach

Transported joint scalar probability density function (PDF) results are presented for ‘Sydney Flame HM3’, a jet type turbulent flame with strong turbulence – chemistry interaction, stabilized behind a bluff body. We apply the novel Reaction-Diffusion Manifold (REDIM) technique, by which a detailed chemistry mechanism is reduced, including diffusion effects. Only N2 and CO2 mass fractions are used as reduced coordinates. A second-moment closure RANS turbulence model is applied. As micro-mixing model, the modified Curl’s coalescence/dispersion (CD) and the Euclidean Minimum Spanning Tree (EMST) models are used. In physical space, agreement between experimental data and simulation results is good up to the neck zone, for the unconditional mean values of velocity, mixture fraction, major and some minor chemical species. Conditional mean profiles in mixture fraction space are also in reasonable agreement with experiments up to the neck zone, though conditional fluctuations tend to be under-predicted. CD generally yields better predictions for the level of fluctuations in mixture fraction space than EMST, but this is partly due to unrealistic particle evolution in composition space. In general, simulations using the REDIM approach for reduction of detailed C2-chemistry confirm earlier findings for micro-mixing model behaviour, obtained with C1-chemistry

Exploiting limited valence patchy particles to understand autocatalytic kinetics

Autocatalysis, i.e., the speeding up of a reaction through the very same molecule which is produced, is common in chemistry, biophysics, and material science. Rate-equation-based approaches are often used to model the time dependence of products, but the key physical mechanisms behind the reaction cannot be properly recognized. Here, we develop a patchy particle model inspired by a bicomponent reactive mixture and endowed with adjustable autocatalytic ability. Such a coarse-grained model captures all general features of an autocatalytic aggregation process that takes place under controlled and realistic conditions, including crowded environments. Simulation reveals that a full understanding of the kinetics involves an unexpected effect that eludes the chemistry of the reaction, and which is crucially related to the presence of an activation barrier. The resulting analytical description can be exported to real systems, as confirmed by experimental data on epoxy-amine polymerizations, solving a long-standing issue in their mechanistic description