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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

Quantal Study of the Exchange Reaction for N + N2 using an ab initio Potential Energy Surface

The N + N2 exchange rate is calculated using a time-dependent quantum dynamics method on a newly determined ab initio potential energy surface (PES) for the ground A" state. This ab initio PES shows a double barrier feature in the interaction region with the barrier height at 47.2 kcal/mol, and a shallow well between these two barriers, with the minimum at 43.7 kcal/mol. A quantum dynamics wave packet calculation has been carried out using the fitted PES to compute the cumulative reaction probability for the exchange reaction of N + N2(J=O). The J - K shift method is then employed to obtain the rate constant for this reaction. The calculated rate constant is compared with experimental data and a recent quasi-classical calculation using a LEPS PES. Significant differences are found between the present and quasiclassical results. The present rate calculation is the first accurate 3D quantal dynamics study for N + N2 reaction system and the ab initio PES reported here is the first such surface for N3.

Wang, Dunyou↗
NASA NTRS1979

F + H2 collisions on two electronic potential energy surfaces - Quantum-mechanical study of the collinear reaction

Collinear quantum calculations are carried out for reactive F + H2 collisions on two electronic potential energy surfaces. The resulting transmission and reflection probabilities exhibit much greater variation with energy than single-surface studies would lead us to anticipate. Transmission to low-lying product channels is increased by orders of magnitude by the presence of the second surface; however, branching ratios among product states are found to be independent of the initial electronic state of the reactants. These apparently contradictory aspects of the calculation are discussed and a tentative explanation put forward to resolve them.

Zimmerman, I. H.↗
NASA NTRS1988

A study of cloud-generated radiative heating and its generation of available potential energy. I - Theoretical background. II - Results for a climatological zonal mean January

The effect of radiative heating and cooling by clouds on the available potential energy (APE) is theoretically discussed. It is shown that the cloud radiative contribution to the generation of APE is determined by the net cloud radiative heating and the efficiency factor, which is a function of the temperature distribution of the atmosphere. Results are presented for low and middle cloud effects for three atmospheric layers. Cloud radiative heating is found to be a single function of cloud optical thickness for all classes designed in terms of cloud top heights and optical thickness. Low clouds at low latitudes destroy APE an midclouds generate APE. A concept is developed to relate the cloud radiative heating to cloud heights and optical depths. Cloud-generated radiative heating is computed for January zonal mean conditions for low and midclouds. For both cases, the strongest influence is found in the low troposphere, with marked differences in signs and magnitudes. At extratropical latitudes, both cloud classes generate net radiative cooling. In the tropics, the effect of low cloud changes from net cooling to the net heating as the optical thickness increases, and midclouds cause net heating. A mechanism is described whereby this dependence produces a strong positive feedback effect on the development of SST anomalies in the tropical oceans.

Stuhlmann, R.↗
DOE OSTI2023

Comprehensive Kinetics on the C 7 H 7 Potential Energy Surface under Combustion Conditions

The automated kinetics workflow code, KinBot, was used to explore and characterize the regions of the C 7 H 7 potential energy surface that are relevant to combustion environments and especially soot inception. We first explored the lowest-energy region, which includes the benzyl, fulvenallene + H, and cyclopentadienyl + acetylene entry points. We then expanded the model to include two higher-energy entry points, vinylpropargyl + acetylene and vinylacetylene + propargyl. The automated search was able to uncover the pathways from the literature. In addition, three important new routes were discovered: a lower-energy pathway connecting benzyl with vinylcyclopentadienyl, a decomposition mechanism from benzyl that results in side-chain hydrogen atom loss to produce fulvenallene + H, and shorter and lower energy routes to the dimethylene-cyclopentenyl intermediates. We systematically reduced the extended model to a chemically relevant domain composed of 63 wells, 10 bimolecular products, 87 barriers, and 1 barrierless channel and constructed a master equation using the CCSD(T)-F12a/cc-pVTZ//ωB97X-D/6-311++G(d,p) level of theory to provide rate coefficients for chemical modeling. Our calculated rate coefficients show excellent agreement with measured ones. We also simulated concentration profiles and calculated branching fractions from the important entry points to provide an interpretation of this important chemical landscape.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

A new diabatic representation of the coupled potential energy surfaces for Na(3p P-2) + H2 yields Na(3s S-2) + H2 or NaH + H

A diabatic representation is presented of the coupled potential-energy surfaces for Na(3p P-2) + H2 yields Na (3s S-2) + H2 or NaH + H. The representation is designed to yield, upon diagonalization, realistic values for the two lowest energy adiabatic states at both asymptotes of the chemical reaction as well as near the conical intersection in the three-body interaction region. It is economical to evaluate and portable. It is suitable for dynamics calculations on both the quenching process and the electronically nonadiabatic chemical reaction.

Halvick, Philippe↗
NASA NTRS1995

Potential energy curves and collision integrals of air components

Collision integrals are fundamental quantities required to determine the transport properties of the environment surrounding aerospace vehicles in the upper atmosphere. These collision integrals can be determined as a function of temperature from the potential energy curves describing the atomic and molecular collisions. Ab initio calculations provide a practical method of computing the required interaction potentials. In this work we will discuss recent advances with an emphasis on the accuracy that is obtainable. Results for interactions, e.g. N+N, N+O, O+O, and H+N2 will be reviewed and their application to the determination of transport properties, such as diffusion and viscosity coefficients, will be examined.

Partridge, Harry↗
NASA NTRS1995

Potential Energy Curves and Collisions Integrals of Air Components: Interactions Involving Ionized Atoms - 2

Collision integrals are fundamental quantities required to determine the transport properties of the environment surrounding aerospace vehicles in the upper atmosphere. These collision integrals can be determined as a function of temperature from the potential energy curves describing the atomic and molecular collisions. Ab initio calculations provide a practical method of computing the required interaction potentials. In this work we will discuss recent advances in scattering calculations with an emphasis on the accuracy that is obtainable. Results for interactions of the atoms and ionized atoms of nitrogen and oxygen will be reviewed and their application to the determination of transport properties, such as diffusion and viscosity coefficients, will be examined.

Stallcop, James R.↗
DOE OSTI2020

Theoretical H + O 3 rate coefficients from ring polymer molecular dynamics on an accurate global potential energy surface: assessing experimental uncertainties

Thermal rate coefficients and kinetic isotope effects have been calculated for an important atmospheric reaction H/D + O 3 → OH/OD + O2 based on an accurate permutation invariant polynomial-neural network potential energy surface, using ring polymer molecular dynamics (RPMD), quasi-classical trajectory (QCT) and variational transition-state theory (VTST) with multidimensional tunneling. The RPMD approach yielded results that are generally in better agreement with experimental rate coefficients than the VTST and QCT ones, especially at low temperatures, attributable to its capacity to capture quantum effects such as tunneling and zero-point energy. Additionally, the theoretical results support one group of existing experiments over the other. In addition, rate coefficients for the D + O 3 → OD + O 2 reaction are also reported using the same methods, which will allow a stringent assessment of future experimental measurements, thus helping to reduce the uncertainty in the recommended rate coefficients of this reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1988

The use of available potential energy to evaluate the impact of satellite data on numerical model analysis during FGGE

To evaluate the effect of the FGGE satellite observing system, the following two data sets were compared by examining the available potential energy (APE) and extratropical cyclone activity within the entire global domain during the first Special Observing Period: (1) the complete FGGE IIIb set, which incorporates satellite soundings, and (2) a NOSAT set which incorporates only conventional data. The time series of the daily total APEs indicate that NOSAT values are larger than the FGGE values, although in the Northern Hemisphere the differences are negligible. Analyses of cyclone scale features revealed only minor differences between the Northern Hemisphere FGGE and NOSAT analyses. On the other hand, substantial differences were revealed in the two Southern Hemisphere analyses, where the satellite soundings apparently add detail to the FGGE set.

Horn, Lyle H.↗
DOE OSTI2024

Exploring the Tl 2H 2 potential energy surface: A comparative analysis with group 13 systems and experiment

Abstract Thallium chemistry is experiencing unprecedented importance. Therefore, it is valuable to characterize some of the simplest thallium compounds. Stationary points along the singlet and triplet TlH potential energy surface have been characterized. Stationary point geometries were optimized with the CCSD(T)/aug‐cc‐pwCVQZ‐PP method. Harmonic vibrational frequencies were computed at the same level of theory while anharmonic vibrational frequencies were computed at the CCSD(T)/aug‐cc‐pwCVTZ‐PP level of theory. Final energetics were obtained with the CCSDT(Q) method. Basis sets up to augmented quintuple‐zeta cardinality (aug‐cc‐pwCV5Z‐PP) were employed to obtain energetics in order to extrapolate to the complete basis set limits using the focal point approach. Zero‐point vibrational energy corrections were appended to the extrapolated energies in order to determine relative energies at 0 K. It was found that the planar dibridged isomer lies lowest in energy while the linear structure lies highest in energy. The results were compared to other group 13 MH (M = B, Al, Ga, In, and Tl) theoretical studies and some interesting variations are found. With respect to experiment, incompatibilities exist.

Chemistry↗
NASA NTRS1991

Converged three-dimensional quantum mechanical reaction probabilities for the F + H2 reaction on a potential energy surface with realistic entrance and exit channels and comparisons to results for three other surfaces

Accurate three-dimensional quantum mechanical reaction probabilities are presented for the reaction F + H2 yields HF + H on the new global potential energy surface 5SEC for total angular momentum J = 0 over a range of translational energies from 0.15 to 4.6 kcal/mol. It is found that the v-prime = 3 HF vibrational product state has a threshold as low as for v-prime = 2.

Lynch, Gillian C.↗
DOE OSTI2025

Two-dimensional ring polymer molecular dynamics determination of the MnO + + H 2 /D 2 reaction rates on a Δ-machine learned potential energy surface

In this work, we investigate the impact of nuclear quantum effects in the kinetics of the MnO + + H 2 reaction, a prototypical system for gas-phase H 2 activation by transition metal oxide ions. The DFT based potential energy surfaces (PESs) for the lowest-lying quintet and septet spin states reported in our previous work are improved by 2953 newly calculated CCSD(T)/AVDZ points using a delta-machine learning (Δ-ML) method. To examine nuclear quantum effects, the rate coefficients are computed using ring-polymer molecular dynamics (RPMD). Due to the mechanistic complexity of the reaction, two reaction coordinates are necessary to map out the free-energy surface and an extended RPMD rate theory is developed. The calculated RPMD rate coefficients on the new PES are in better agreement with experimental data. The calculated kinetic isotope effects (KIEs) range from 1.6 to 1.8, also in good agreement with the experimental values. Additionally, the converged RPMD rate coefficients are 2.3 to 3.1 times higher than their classical counterparts across the studied temperature range, suggesting the presence of moderate nuclear quantum effects in this reaction.

Liu, Yang [University of New Mexico, Albuquerque, ↗
NASA NTRS1990

Assessing the impact of different satellite retrieval methods on forecast available potential energy

The effects of the inclusion of satellite temperature retrieval data, and of different satellite retrieval methods, on forecasts made with the NASA Goddard Laboratory for Atmospheres (GLA) fourth-order model were investigated using, as the parameter, the available potential energy (APE) in its isentropic form. Calculation of the APE were used to study the differences in the forecast sets both globally and in the Northern Hemisphere during 72-h forecast period. The analysis data sets used for the forecasts included one containing the NESDIS TIROS-N retrievals, the GLA retrievals using the physical inversion method, and a third, which did not contain satellite data, used as a control; two data sets, with and without satellite data, were used for verification. For all three data sets, the Northern Hemisphere values for the total APE showed an increase throughout the forecast period, mostly due to an increase in the zonal component, in contrast to the verification sets, which showed a steady level of total APE.

Whittaker, Linda M.↗
NASA NTRS2000

Effective Potential Energies and Transport Cross Sections for Interactions of Hydrogen and Nitrogen

The interaction energies for N2-He and N2-H2 are calculated by accurate ab initio methods. The virial coefficient and differential scattering cross section for N2-H2 are calculated; the theoretical results are compared with experimental data. The transport collision integrals for N2-H2 and N2-N2 interactions are calculated and tabulated; the results yield transport coefficients that compare well with measured data. Transport coefficients are found to be determined accurately from the interaction energies for a specific configuration of the molecule formed from the interaction partners. Comparisons with results of measurement and accurate calculations demonstrate that the transport properties of complex molecular interactions can be determined rapidly and fairly accurately from the interaction energies of simpler system using combination rules for the short-range parameters of effective interaction energies and the coefficients for the long-range forces. The coefficients for a two-parameter temperature expansion of diffusion and viscosity are tabulated for a realistic universal potential energy that is based primarily on the results of very accurate calculations of the He-He interaction energy.

Stallcop, James R.↗
DOE OSTI2023

Comparison of multifidelity machine learning models for potential energy surfaces

Multifidelity modeling is a technique for fusing the information from two or more datasets into one model. It is particularly advantageous when one dataset contains few accurate results and the other contains many less accurate results. Within the context of modeling potential energy surfaces, the low-fidelity dataset can be made up of a large number of inexpensive energy computations that provide adequate coverage of the N-dimensional space spanned by the molecular internal coordinates. The high-fidelity dataset can provide fewer but more accurate electronic energies for the molecule in question. Here, we compare the performance of several neural network-based approaches to multifidelity modeling. We show that the four methods (dual, Δ-learning, weight transfer, and Meng–Karniadakis neural networks) outperform a traditional implementation of a neural network, given the same amount of training data. We also show that the Δ-learning approach is the most practical and tends to provide the most accurate model.

Chemistry↗
NASA NTRS1988

Computed potential energy surfaces for chemical reactions

The minimum energy path for the addition of a hydrogen atom to N2 is characterized in CASSCF/CCI calculations using the (4s3p2d1f/3s2p1d) basis set, with additional single point calculations at the stationary points of the potential energy surface using the (5s4p3d2f/4s3p2d) basis set. These calculations represent the most extensive set of ab initio calculations completed to date, yielding a zero point corrected barrier for HN2 dissociation of approx. 8.5 kcal mol/1. The lifetime of the HN2 species is estimated from the calculated geometries and energetics using both conventional Transition State Theory and a method which utilizes an Eckart barrier to compute one dimensional quantum mechanical tunneling effects. It is concluded that the lifetime of the HN2 species is very short, greatly limiting its role in both termolecular recombination reactions and combustion processes.

Walch, Stephen P.↗
NASA NTRS1972

Collision matrix elements near a pseudocrossing of potential energy curves.

The cross sections of certain inelastic atomic collision processes can be determined from the matrix elements of the collision operator, d/dR, where R is the separation of the colliding atoms. At one extreme, the matrix element may pass through zero near a pseudocrossing of potential energy curves, while at the other extreme, it may pass through a maximum. The resulting cross sections are entirely different in magnitude and in energy dependence. An attempt is made to predict the qualitative behavior of the collision matrix elements with variations in R from an analysis of the Born-Oppenheimer adiabatic Hamiltonian. The modifications caused by a second pseudocrossing with a third adiabatic state are studied.

Oppenheimer, M.↗