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Results for “Polarizable continuum model”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
NASA NTRS2011

A Theoretical Investigation of the Plausibility of Reactions Between Ammonia and Carbonyl Species (Formaldehyde, Acetaldehyde, and Acetone) in Interstellar Ice Analogs at Ultracold Temperatures

We have reexamined the reaction between formaldehyde and ammonia, which was previously studied by us and other workers in modestly sized cluster calculations. Larger model systems with up to 12H2O were employed, and reactions of two more carbonyl species, acetaldehyde and acetone, were also carried out. Calculations were performed at the B3LYP/6-31+G** level with bulk solvent effects treated with a polarizable continuum model; limited MP2/6-31+G** calculations were also performed. We found that while the barrier for the concerted proton relay mechanism described in previous work remains modest, it is still prohibitively high for the reaction to occur under the ultracold conditions that prevail in dense interstellar clouds. However, a new pathway emerged in more realistic clusters that involves at least one barrierless step for two of the carbonyl species considered here: ammonia reacts with formaldehyde and acetaldehyde to form a partial charge transfer species in small clusters (4H2O) and a protonated hydroxyamino intermediate species in large clusters (9H2O, 12H2O); modest barriers that decrease sharply with cluster size are found for the analogous processes for the acetone-NH3 reaction. Furthermore, if a second ammonia replaces one of the water molecules in calculations in the 9H2O clusters, deprotonation can occur to yield the same neutral hydroxyamino species that is formed via the original concerted proton relay mechanism. In at least one position, deprotonation is barrierless when zero-point energy is included. In addition to describing the structures and energetics of the reactions between formaldehyde, acetaldehyde, and acetone with ammonia, we report spectroscopic predictions of the observable vibrational features that are expected to be present in ice mixtures of different composition.

Chen, Lina↗
NASA NTRS1988

Differential oscillator strengths and dipole polarizabilities for transitions of the helium sequence

The dipole radial integral for an initial discrete 1s state and a final continuum state has been calculated under the screened hydrogenic model. In this model, single-electron hydrogenic wave functions are employed, and the initial and the final states are treated by two different effective-charge parameters. Numerical values of differential oscillator strengths for transitions from 1s2 1S to the continuum for the helium sequence ions are obtained. Also calculated are the dipole polarizabilities, which are found to be in excellent agreement with the results of other authors.

Khan, F.↗
NASA NTRS1999

Effective Forces Between Colloidal Particles

Colloidal suspensions have proven to be excellent model systems for the study of condensed matter and its phase behavior. Many of the properties of colloidal suspensions can be investigated with a systematic variation of the characteristics of the systems and, in addition, the energy, length and time scales associated with them allow for experimental probing of otherwise inaccessible regimes. The latter property also makes colloidal systems vulnerable to external influences such as gravity. Experiments performed in micro-ravity by Chaikin and Russell have been invaluable in extracting the true behavior of the systems without an external field. Weitz and Pusey intend to use mixtures of colloidal particles with additives such as polymers to induce aggregation and form weak, tenuous, highly disordered fractal structures that would be stable in the absence of gravitational forces. When dispersed in a polarizable medium, colloidal particles can ionize, emitting counterions into the solution. The standard interaction potential in these charged colloidal suspensions was first obtained by Derjaguin, Landau, Verwey and Overbeek. The DLVO potential is obtained in the mean-field linearized Poisson-Boltzmann approximation and thus has limited applicability. For more precise calculations, we have used ab initio density functional theory. In our model, colloidal particles are charged hard spheres, the counterions are described by a continuum density field and the solvent is treated as a homogeneous medium with a specified dielectric constant. We calculate the effective forces between charged colloidal particles by integrating over the solvent and counterion degrees of freedom, taking into account the direct interactions between the particles as well as particle-counterion, counterion-counterion Coulomb, counterion entropic and correlation contributions. We obtain the effective interaction potential between charged colloidal particles in different configurations. We evaluate two- and three-body forces in the bulk as well as study the influence of soft walls. We qualitatively explain the effects of the walls on the forces and demonstrate that many-body effects are negligible in our system. With adjustments in the parameters, the DLVO pair-potential can describe the results quantitatively. Besides electrostatic interactions, entropic depletion effects that arise from (hard-core) exclusion play an important role in determining the behavior of multi-component colloidal suspensions. A standard theory for depletion forces is due to Asakura and Oosawa and is based on the ideal gas approximation. To go beyond this approximation, we have studied entropic forces in molecular dynamics simulations of systems of hard spheres (the effects of the solvent have been ignored). The effective depletion forces for these systems can be found either from equilibrium distribution functions or from direct momentum transfer calculations. Our results obtained by either method show qualitative differences from the Asakura-Oosawa forces, indicating a longer range, higher value at contact and most importantly a more complicated structure, comprising of several maxima and minima. Our calculations include the determination of effective forces between two spheres, a hard sphere and a wall, and the behavior of a hard sphere near a step-edge and a corner. We also demonstrate that such entropic forces do not necessarily satisfy pairwise additivity.

Tehver, Riina↗
NASA NTRS2022

Recommended Direct Simulation Monte Carlo Collision Model Parameters for Reacting Methane Flows

While hydrocarbon combustion and gas-surface interactions have been simulated for a variety of applications in continuum solvers, such processes have been rarely investigated in Direct Simulation Monte Carlo (DSMC). Thus Variable Hard/Soft Sphere (VHS/VSS)collision parameters are not available for most molecules of interest in the decomposition of methane, a significant pyrolysis gas product and potential atmospheric species for Titan re-entries. As these properties are essential for accurate modeling of gas transport and thermochemical effects, a method must be devised to compute them for use in DSMC. In this study, the methodology outlined in Stephani et al is utilized to compute the VHS/VSS parameters by fitting the Ω(1,1)and Ω(2,2) collision integrals [1]. These collision integrals are typically computed from intermolecular potentials and are used in CFD simulations to calculate transport properties such as viscosity, thermal conductivity, and diffusion. This approach ensures consistency between micro-scale collisions and macro-scale transport properties. To produce the necessary collision integrals needed for the fitting routine, we utilize the method described by Laricchiuta et al, where collision integrals are computed based on the constituent particles’ polarizability and effective electron number [2].Preliminary computations of pure-species Ω(1,1)and Ω(2,2)collision integrals produced from the coupled approach of Stephani et al and Laricchiuta et al for methane show good agreement with those computed via available ab-initio Potential Energy Surface Computations, as seen in Figure 1. Above 300K, no more than 12% deviation is observed between the two results over the temperature range of the fitted PES data [3].Current results of this study include full collision-specificVSS transport properties for a complex-species mixture involving major byproducts of pure methane decomposition. Targeted final results will include a comprehensive list of VSS parameters relevant toDSMC simulations of Titan atmospheric entry, based on the reduced kinetic model of Savajano et al [4].

M R Gosma↗