On the heat capacity of adsorbed phases using molecular simulation

The heat capacities of argon, ammonia, and methanol on carbon black at 87.3, 240, and 300 K, respectively, have been investigated. The carbon black surface has been modeled with and without carbonyl groups. Part of this investigation is a decomposition of the heat capacity into its contributions from the different interaction potentials of an adsorption system. All systems show a spectrum of heat capacity versus loading, and this behavior depends on the carbonyl configuration present on the surface. For methanol and ammonia the variation of the heat capacity between the two for the same carbonyl configurations is greater than the variation in the heat of adsorption. Heat capacities of methanol and ammonia are generally dominated by fluid-fluid interactions due to the strong association of fluid particles through hydrogen bonding. The difference in the heat capacity behavior of the two fluids is an indicator of their different clustering behaviors on the carbon black surface. The presence of carbonyl groups reduces the fluid-fluid contributions to the heat capacity. This is due to the compensation of fluid-fluid interactions with fluid-functional group interactions. At 87.3 K a first layer transition to a solidlike state is present for argon and results in a large peak in the heat capacity on a bare surface. The presence of functional groups greatly reduces this peak in the heat capacity by disrupting the packing of argon on the surface and preventing a transition to a solidlike state. (c) 2007 American Institute of Physics

Multilayer modeling of porous grain surface chemistry I. The GRAINOBLE model

Mantles of iced water, mixed with CO, H2CO, and CH3OH are formed during the so called prestellar core phase. In addition, radicals are also thought to be formed on the grain surfaces, and to react to form complex organic molecules later on, during the warm-up phase of the protostellar evolution. We aim to study the formation of the grain mantles during the prestellar core phase and the abundance of H2CO, CH3OH, and radicals trapped in them. We have developed a macrosopic statistic multilayer model that follows the formation of grain mantles with time and that includes two effects that may increase the number of radicals trapped in the mantles: i) at each time of the mantle formation, only the surface layer is chemically active rather than the entire bulk, and ii) the porous structure of grains allows to trap reactive particles. The model considers a network of H, O and CO forming neutral species such as water, CO, formaldehyde, and methanol, plus several radicals. We run a large grid of models to study the impact of the mantle multilayer nature and grain porous structure. In addition, we explored the influence of the uncertainty of other key parameters on the mantle composition. Our model predicts relatively large abundances of radicals. In addition, the multilayer approach makes it possible to follow the chemical differentiation within the grain mantle, showing that the mantles are far from being uniform. For example, methanol is mostly present in the outer layers of the mantles whereas CO and other reactive species are trapped in the inner layers. The overall mantle composition depends on the density and age of the prestellar core, and on some microscopic parameters. Comparison with observations allows us to constrain the value of few parameters and provide some indications on the physical conditions during the formation of the ices.Comment: 20 pages and 19 figures. Accepted in Astronomy & Astrophysic

The Interaction of Rare Gas Atoms with Graphite Surfaces. I. Single Adatom Energies

The Gordon-Kim local density method is applied to the calculation of the interaction energy of helium, neon, argon, and krypton with the basal plane of graphite. In all cases, the binding site is found to be above the center of a hexagon, but the barrier to migration to other sites is less than 50 cal/ mole. Comparisons are made with other studies on these systems, and the role of non-two-body additive effects is discussed

Including screening in van der Waals corrected density functional theory calculations: The case of atoms and small molecules physisorbed on graphene

The DFT/vdW-QHO-WF method, recently developed to include the van der Waals (vdW) interactions in approximated Density Functional Theory (DFT) by combining the Quantum Harmonic Oscillator model with the Maximally Localized Wannier Function technique, is applied to the cases of atoms and small molecules (X=Ar, CO, H$_2$, H$_2$O) weakly interacting with benzene and with the ideal planar graphene surface. Comparison is also presented with the results obtained by other DFT vdW-corrected schemes, including PBE+D, vdW-DF, vdW-DF2, rVV10, and by the simpler Local Density Approximation (LDA) and semilocal Generalized Gradient Approximation (GGA) approaches. While for the X-benzene systems all the considered vdW-corrected schemes perform reasonably well, it turns out that an accurate description of the X-graphene interaction requires a proper treatment of many-body contributions and of short-range screening effects, as demonstrated by adopting an improved version of the DFT/vdW-QHO-WF method. We also comment on the widespread attitude of relying on LDA to get a rough description of weakly interacting systems