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All sourcesNASA NTRSDOE OSTI
NASA NTRS2016

The Effects of Consistent Chemical Kinetics Calculations on the Pressure-Temperature Profiles and Emission Spectra of Hot Jupiters

In this work we investigate the impact of calculating non-equilibrium chemical abundances consistently with the temperature structure for the atmospheres of highly-irradiated, close-in gas giant exoplanets. Chemical kinetics models have been widely used in the literature to investigate the chemical compositions of hot Jupiter atmospheres which are expected to be driven away from chemical equilibrium via processes such as vertical mixing and photochemistry. All of these models have so far used pressure-temperature (P-T) profiles as fixed model input. This results in a decoupling of the chemistry from the radiative and thermal properties of the atmosphere, despite the fact that in nature they are intricately linked. We use a one-dimensional radiative-convective equilibrium model, ATMO, which includes a sophisticated chemistry scheme to calculate P-T profiles which are fully consistent with non-equilibrium chemical abundances, including vertical mixing and photochemistry. Our primary conclusion is that, in cases of strong chemical disequilibrium, consistent calculations can lead to differences in the P-T profile of up to 100 K compared to the P-T profile derived assuming chemical equilibrium. This temperature change can, in turn, have important consequences for the chemical abundances themselves as well as for the simulated emission spectra. In particular, we find that performing the chemical kinetics calculation consistently can reduce the overall impact of non-equilibrium chemistry on the observable emission spectrum of hot Jupiters. Simulated observations derived from non-consistent models could thus yield the wrong interpretation. We show that this behaviour is due to the non-consistent models violating the energy budget balance of the atmosphere.

planets and satellites↗
NASA NTRS1976

Non-equilibrium radiation from viscous chemically reacting two-phase exhaust plumes

A knowledge of the structure of the rocket exhaust plumes is necessary to solve problems involving plume signatures, base heating, plume/surface interactions, etc. An algorithm is presented which treats the viscous flow of multiphase chemically reacting fluids in a two-dimensional or axisymmetric supersonic flow field. The gas-particle flow solution is fully coupled with the chemical kinetics calculated using an implicit scheme to calculate chemical production rates. Viscous effects include chemical species diffusion with the viscosity coefficient calculated using a two-equation turbulent kinetic energy model.

Penny, M. M.↗
NASA NTRS1991

Quantum mechanical calculations to chemical accuracy

The accuracy of current molecular-structure calculations is illustrated with examples of quantum mechanical solutions for chemical problems. Two approaches are considered: (1) the coupled-cluster singles and doubles (CCSD) with a perturbational estimate of the contribution of connected triple excitations, or CCDS(T); and (2) the multireference configuration-interaction (MRCI) approach to the correlation problem. The MRCI approach gains greater applicability by means of size-extensive modifications such as the averaged-coupled pair functional approach. The examples of solutions to chemical problems include those for C-H bond energies, the vibrational frequencies of O3, identifying the ground state of Al2 and Si2, and the Lewis-Rayleigh afterglow and the Hermann IR system of N2. Accurate molecular-wave functions can be derived from a combination of basis-set saturation studies and full configuration-interaction calculations.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1986

Horizontal mixing coefficients for two-dimensional chemical models calculated from National Meteorological Center Data

Calculations of the two-dimensional, species-independent mixing coefficients for two-dimensional chemical models for the troposphere and stratosphere are performed using quasi-geostrophic potential vorticity fluxes and gradients from 4 years of National Meteorological Center data for the four seasons in both hemispheres. Results show that the horizontal mixing coefficient values for the winter lower stratosphere are broadly consistent with those currently employed in two-dimensional models, but the horizontal mixing coefficient values in the northern winter upper stratosphere are much larger than those usually used.

Newman, P. A.↗
NASA NTRS1979

Metastable isomers - A new class of interstellar molecules

The abundances of a variety of metastable isomers of small organic molecules, analogous to HNC/HCN, in dense interstellar clouds are considered. These metastable species, some of which are thought to exist as intermediates in laboratory organic chemical reactions, are of considerable interest to chemists. Current ideas of gas-phase, ion-molecule chemistry are utilized to demonstrate that such metastable species should often be present in dense clouds in sufficient abundance to be observed. Unfortunately, the spectral constants of metastable isomers have rarely been determined in the laboratory, and quantum chemical calculations of a varying degree of accuracy must be utilized; results are included of some new quantum chemical calculations. The interstellar chemistry and expected microwave spectra of a representative sample of possibly important interstellar metastable isomers are discussed.

Green, S.↗
NASA NTRS1993

Applicability of PM3 to transphosphorylation reaction path: Toward designing a minimal ribozyme

A growing body of evidence shows that RNA can catalyze many of the reactions necessary both for replication of genetic material and the possible transition into the modern protein-based world. However, contemporary ribozymes are too large to have self-assembled from a prebiotic oligonucleotide pool. Still, it is likely that the major features of the earliest ribozymes have been preserved as molecular fossils in the catalytic RNA of today. Therefore, the search for a minimal ribozyme has been aimed at finding the necessary structural features of a modern ribozyme (Beaudry and Joyce, 1990). Both a three-dimensional model and quantum chemical calculations are required to quantitatively determine the effects of structural features of the ribozyme on the reaction it catalyzes. Using this model, quantum chemical calculations must be performed to determine quantitatively the effects of structural features on catalysis. Previous studies of the reaction path have been conducted at the ab initio level, but these methods are limited to small models due to enormous computational requirements. Semiempirical methods have been applied to large systems in the past; however, the accuracy of these methods depends largely on a simple model of the ribozyme-catalyzed reaction, or hydrolysis of phosphoric acid. We find that the results are qualitatively similar to ab initio results using large basis sets. Therefore, PM3 is suitable for studying the reaction path of the ribozyme-catalyzed reaction.

Manchester, John I.↗
NASA NTRS1986

The efficient calculation of chemically reacting flow

A semi-implicit finite volume formulation is used to study flows with chemical reactions. In this formulation the source terms resulting from the chemical reactions are treated implicitly and the resulting system of partial differential equations is solved using two time-stepping schemes. The first is based on the Runge-Kutta method while the second is based on an Adams predictor-corrector method. Results show that improvements in computational efficiency depend to a large extent on the manner in which the source term is treated. Further, analysis and computation indicate that the Runge-Kutta method is more efficient than the Adams methods. Finally, an adaptive time stepping scheme is developed to study problems involving shock ignition. Calculations for a hydrogen-air system agree well with other methods.

Eklund, D. R.↗
DOE OSTI2026

Activation of methane by U + studied by guided ion beam tandem mass spectrometry and quantum chemistry

Reaction pathways of all products formed in the U + + CH 4 (CD 4 ) reaction were explored as a function of kinetic energy using guided ion beam tandem mass spectrometry and quantum chemical calculations. UH + , UC + , UCH + , UCH 2 + , and UCH 3 + (and their perdeuterated analogues) are formed in endothermic reactions. In both systems, the UCH 2 + (UCD 2 + ) dehydrogenated product was the dominant product in the low-energy region, whereas the UH + (UD + ) hydride product became predominant at high energies. The kinetic energy behavior of the various products is consistent with a common intermediate of H–U + –CH 3 (D–U + –CD 3 ). Here, the kinetic energy dependence of all product cross sections was modeled to obtain experimental bond dissociation energies at 0 K (in eV): D 0 (U + –H) = 2.42 ± 0.10, D 0 (U + –C) = 3.95 ± 0.12, D 0 (U + –CH) = 4.91 ± 0.09, D 0 (U + –CH 2 ) = 4.11 ± 0.04, and D 0 (U + –CH 3 ) = 2.41 ± 0.09. Quantum chemical calculations using the UCCSD(T) and UB3LYP approaches with the cc-pwCVXZ-PP basis set with MDF-60 pseudopotential for U + and the aug-cc-pCVXZ and aug-cc-pVXZ (X = T, Q) basis set for carbon and hydrogen, respectively, validate the experimental bond dissociation energies and outline the potential energy surface for all reactions observed. In addition, spin–orbit corrections of the bond energies for all products were calculated at a CASSCF-CASPT2-RASSI level.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

CET93 and CETPC: An interim updated version of the NASA Lewis computer program for calculating complex chemical equilibria with applications

The NASA Lewis chemical equilibrium program with applications continues to be improved and updated. The latest version is CET93. This code, with smaller arrays, has been compiled for use on an IBM or IBM-compatible personal computer and is called CETPC. This report is intended to be primarily a users manual for CET93 and CETPC. It does not repeat the more complete documentation of earlier reports on the equilibrium program. Most of the discussion covers input and output files, two new options (ONLY and comments), example problems, and implementation of CETPC.

Mcbride, Bonnie J.↗
NASA NTRS1990

The chemical effects of the Martian environment on power system component materials: A theoretical approach

In the foreseeable future, an expedition may be undertaken to explore the planet Mars. Some of the power source options being considered for such a mission are photovoltaics, regenerative fuel cells and nuclear reactors. In addition to electrical power requirements, environmental conditions en route to Mars, in the planetary orbit and on the Martian surface must be simulated and studied in order to anticipate and solve potential problems. Space power systems components such as photovoltaic arrays, radiators, and solar concentrators may be vulnerable to degradation in the Martian environment. Natural characteristics of Mars which may pose a threat to surface power systems include high velocity winds, dust, ultraviolet radiation, large daily variation in temperature, reaction to components of the soil, atmosphere and atmospheric condensates as well as synergistic combinations. Most of the current knowledge of the characteristics of the Martian atmosphere and soil composition was obtained from the Viking 1 and 2 missions in 1976. A theoretical study is presented which was used to assess the effects of the Martian atmospheric conditions on the power systems components. A computer program written at NASA-Lewis for combustion research that uses a free energy minimization technique was used to calculate chemical equilibrium for assigned thermodynamic states of temperature and pressure. The power system component materials selected for this study include: silicon dioxide, silicon, carbon, copper, and titanium. Combinations of environments and materials considered include: (1) Mars atmosphere with power surface material, (2) Mars atmosphere and dust component with power surface material, and (3) Mars atmosphere and hydrogen peroxide or superoxide or superoxide with power system material. The chemical equilibrium calculations were performed at a composition ratio (oxidant to reactant) of 100. The temperature for the silicon dioxide material and silicon, which simulate photovoltaic cells, were 300 and 400 K; for carbon, copper and titanium, which simulate radiator surfaces, 300, 500, and 1000 K. All of the systems were evaluated at pressures of 700, 800, and 900 Pa, which stimulate the Martian atmosphere.

Perez-Davis, Marla E.↗
NASA NTRS1991

Calculations on the rate of the ion-molecule reaction between NH3(+) and H2

The rate coefficient for the ion-molecule reaction NH3(+) + H2 yields NH4(+) + H has been calculated as a function of temperature with the use of the statistical phase space approach. The potential surface and reaction complex and transition state parameters used in the calculation have been taken from ab initio quantum chemical calculations. The calculated rate coefficient has been found to mimic the unusual temperature dependence measured in the laboratory, in which the rate coefficient decreases with decreasing temperature until 50-100 K and then increases at still lower temperatures. Quantitative agreement between experimental and theoretical rate coefficients is satisfactory given the uncertainties in the ab initio results and in the dynamics calculations. The rate coefficient for the unusual three-body process NH3(+) + H2 + He yields NH4(+) + H + He has also been calculated as a function of temperature and the result found to agree well with a previous laboratory determination.

Herbst, Eric↗