Molecular Physics of Elementary Processes relevant to Hypersonics: atom-molecule, molecule-molecule and atom-surface processes.

In the present chapter some prototype gas and gas-surface processes occurring within the hypersonic flow layer surrounding spacecrafts at planetary entry are discussed. The discussion is based on microscopic dynamical calculations of the detailed cross sections and rate coefficients performed using classical mechanics treatments for atoms, molecules and surfaces. Such treatment allows the evaluation of the efficiency of thermal processes (both at equilibrium and nonequilibrium distributions) based on state-to-state and state specific calculations properly averaged over the population of the initial states. The dependence of the efficiency of the considered processes on the initial partitioning of energy among the various degrees of freedom is discussed

Atomic and molecular data for spacecraft re-entry plasmas

The modeling of atmospheric gas, interacting with the space vehicles in re-entry conditions in planetary exploration missions, requires a large set of scattering data for all those elementary processes occurring in the system. A fundamental aspect of re-entry problems is represented by the strong non-equilibrium conditions met in the atmospheric plasma close to the surface of the thermal shield, where numerous interconnected relaxation processes determine the evolution of the gaseous system towards equilibrium conditions. A central role is played by the vibrational exchanges of energy, so that collisional processes involving vibrationally excited molecules assume a particular importance. In the present paper, theoretical calculations of complete sets of vibrationally state-resolved cross sections and rate coefficients are reviewed, focusing on the relevant classes of collisional processes: resonant and non-resonant electron-impact excitation of molecules, atom-diatom and molecule-molecule collisions as well as gas-surface interaction. In particular, collisional processes involving atomic and molecular species, relevant to Earth (N2, O2, NO), Mars (CO2, CO, N2) and Jupiter (H2, He) atmospheres are considered

Full Dimensional Potential Energy Function and Calculation of State-Specific Properties of the CO+N2 Inelastic Processes Within an Open Molecular Science Cloud Perspective

A full dimensional Potential Energy Surface (PES) of the CO + N2 system has been generated by extending an approach already reported in the literature and applied to N2-N2 (Cappelletti et al., 2008), CO2-CO2 (Bartolomei et al., 2012), and CO2-N2 (Lombardi et al., 2016b) systems. The generation procedure leverages at the same time experimental measurements and high-level ab initio electronic structure calculations. The procedure adopts an analytic formulation of the PES accounting for the dependence of the electrostatic and non-electrostatic components of the intermolecular interaction on the deformation of the monomers. In particular, the CO and N2 molecular multipole moments and electronic polarizabilities, the basic physical properties controlling the behavior at intermediate and long-range distances of the interaction components, were made to depend on relevant internal coordinates. The formulated PES exhibits substantial advantages when used for structural and dynamical calculations. This makes it also well suited for reuse in Open Molecular Science Cloud services

Atomic and molecular data for spacecraft re-entry plasmas

The modeling of atmospheric gas, interacting with the space vehicles in re-entry conditions in planetary exploration missions, requires a large set of scattering data for all those elementary processes occurring in the system. A fundamental aspect of re-entry problems is represented by the strong non-equilibrium conditions met in the atmospheric plasma close to the surface of the thermal shield, where numerous interconnected relaxation processes determine the evolution of the gaseous system towards equilibrium conditions. A central role is played by the vibrational exchanges of energy, so that collisional processes involving vibrationally excited molecules assume a particular importance. In the present paper, theoretical calculations of complete sets of vibrationally state-resolved cross sections and rate coefficients are reviewed, focusing on the relevant classes of collisional processes: resonant and non-resonant electron-impact excitation of molecules, atom-diatom and molecule-molecule collisions as well as gas-surface interaction. In particular, collisional processes involving atomic and molecular species, relevant to Earth (N-2, O-2, NO), Mars (CO2, CO, N-2) and Jupiter (H-2, He) atmospheres are considered

Heat Conductivity of Polyatomic and Polar Gases and Gas Mixtures

Theory for calculating heat conductivity of polyatomic and polar gases and gas mixture

Assessment of high-fidelity collision models in the direct simulation Monte Carlo method

Advances in computer technology over the decades has allowed for more complex physics to be modeled in the DSMC method. Beginning with the first paper on DSMC in 1963, 30,000 collision events per hour were simulated using a simple hard sphere model. Today, more than 10 billion collision events can be simulated per hour for the same problem. Many new and more physically realistic collision models such as the Lennard-Jones potential and the forced harmonic oscillator model have been introduced into DSMC. However, the fact that computer resources are more readily available and higher-fidelity models have been developed does not necessitate their usage. It is important to understand how such high-fidelity models affect the output quantities of interest in engineering applications. The effect of elastic and inelastic collision models on compressible Couette flow, ground-state atomic oxygen transport properties, and normal shock waves have therefore been investigated. Recommendations for variable soft sphere and Lennard-Jones model parameters are made based on a critical review of recent ab-initio calculations and experimental measurements of transport properties

Water vapor diffusion in Mars subsurface environments

The diffusion coefficient of water vapor in unconsolidated porous media is measured for various soil simulants at Mars-like pressures and subzero temperatures. An experimental chamber which simultaneously reproduces a low-pressure, low-temperature, and low-humidity environment is used to monitor water flux from an ice source through a porous diffusion barrier. Experiments are performed on four types of simulants: 40–70 µm glass beads, sintered glass filter disks, 1–3 µm dust (both loose and packed), and JSC Mars–1. A theoretical framework is presented that applies to environments that are not necessarily isothermal or isobaric. For most of our samples, we find diffusion coefficients in the range of 2.8 to 5.4 cm^2 s^-1 at 600 Pascal and 260 K. This range becomes 1.9–4.7 cm^2 s^-1 when extrapolated to a Mars-like temperature of 200 K. Our preferred value for JSC Mars–1 at 600 Pa and 200 K is 3.7 ± 0.5 cm^2 s^-1. The tortuosities of the glass beads is about 1.8. Packed dust displays a lower mean diffusion coefficient of 0.38 ± 0.26 cm^2 s^-1, which can be attributed to transition to the Knudsen regime where molecular collisions with the pore walls dominate. Values for the diffusion coefficient and the variation of the diffusion coefficient with pressure are well matched by existing models. The survival of shallow subsurface ice on Mars and the providence of diffusion barriers are considered in light of these measurements

Kinetic Models of Oxygen Thermochemistry Based on Quasi-Classical Trajectory Analysis

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/140704/1/1.T4968.pd

Study of vibrational excitation mechanisms of CO2 at high temperatures

Calculating vibrational excitation of CO2 for anharmonic coupling and normal mode at high temperatur

Dynamics on Multiple Potential Energy Surfaces: Quantitative Studies of Elementary Processes Relevant to Hypersonics

The determination of thermal and vibrational relaxation rates of triatomic systems suitable for application in hypersonic model calculations is discussed. For this, potential energy surfaces for ground and electronically excited state species need to be computed and represented with high accuracy and quasiclassical or quantum nuclear dynamics simulations provide the basis for determining the relevant rates. These include thermal reaction rates, state-to-state cross-sections, or vibrational relaxation rates. For exemplary systems - [NNO], [NOO], and [CNO] - all individual steps are described and a literature overview for them is provided. Finally, as some of these quantities involve considerable computational expense, for the example of state-to-state cross sections the construction of an efficient model based on neural networks is discussed. All such data is required and being used in more coarse-grained computational fluid dynamics simulations.Comment: Review article, 46 pages, 8 figure