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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 NTRS1983

The response of stationary planetary waves to tropospheric forcing

The lower boundary forcing of airflow over topography, and the internal forcing that results from the geographical distribution of diabatic heating, are studied in light of a steady state, linear, quasi-geostrophic model of stationary waves on a sphere. The lower boundary vertical motions forced by airflow over topography depend on whether the horizontal deflection of airflow around topographic features is taken into account, the level of the wind profile at which flow over topography is assumed to take place, and the topographic data set that was used in the forcing formulation. The lower boundary forcing is taken to be given by the observed stationary planetary wave in lower boundary geopotential height, and the internal forcing is computed using the planetary wave propagation equation on the observed wave structure.

Alpert, J. C.↗
NASA NTRS1985

The form of Newtonian cooling in atmospheric tidal theory

The analytical results of Zurek (1986) are applied to compare the vertical-structure equations obtained by Dickinson and Geller (1968) and Lindzen and McKenzie (1967) in solving the classical tidal equations for planetary atmospheres when Newtonian cooling (NC) is included as part of diabatic tidal forcing. The two diabatic forcings are found to be different when the basic state temperature varies with height, and it is recommended that a log-pressure NC formulation be used whenever temperature is made a function of pressure in the radiative-damping calculation. Scaling arguments are presented to show that the choice of NC formulation has significant effects only in cases where the radiative time constants are short (such as the thin CO2 atmosphere of Mars). Numerical computations for that case indicate a difference of 20 percent in amplitude and 15 deg in phase for the (probably meteorologically significant) 4.1-d wavenumber-one Rossby tidal mode.

Zurek, Richard W.↗
DOE OSTI2026

Diabatization with Electrostatic Embedding for Studying Photophysics in Organic Molecular Crystals

Highly emissive organic molecular crystals find applications in several areas, such as organic electronics, solar cells, and sensors. Understanding the excited-state mechanisms underlying these applications is essential for optimizing and controlling them effectively. Exciton models coupled with nonadiabatic dynamics, particularly quantum dynamics, provide crucial insights into photochemical and photophysical processes in molecular crystals. Nevertheless, there remains a lack of general tools and automated workflows to facilitate such simulations. In this paper, we present a computational strategy to investigate the photoactivated dynamics of organic molecular crystals, bridging methodologies traditionally used for molecular systems and materials science, with a particular focus on the interplay between local excitations and charge transfer (CT) processes. We have implemented an interface between the fromage and Overdia programs, enabling the construction of vibronic Hamiltonians for molecular crystals within an excited-state ONIOM(QM:QM′) framework, incorporating long-range electrostatics through a RESP-based Ewald summation. Fragment-based diabatization provides a route to quantum dynamics simulations in weak-to-intermediate coupling regimes. The method was applied to the photophysics of dibenzo[g,p]chrysene (DBC) crystals using time-dependent DFT. The fromage/ Overdia interface was employed to compute the couplings of local excitations and CT states for 18 unique DBC dimers in the crystal and to quantify the influence of electrostatic embedding, which was found to be modest (10−20%). Simulations on π-stacked dimers reproduced the small red shift observed experimentally from solution to crystal, attributed to electronic interactions among fixed monomers rather than crystal electrostatics. Quantum dynamics simulations revealed ultrafast population transfer from bright local excitations to CT states. This approach establishes a robust framework linking molecular and solid-state excited-state dynamics, with potential applications for studying excitations, defects, and impurities in molecular crystals.

Crystals↗
DOE OSTI2026

Mapping Rydberg States of H 2 with the Halfium R-Matrix Method

In this article, we use the Halfium R-matrix method to investigate the Rydberg states of the H 2 molecule up to n = 20, filling the gap above the low-lying bound states already calculated with configuration interaction packages. Moreover, we show that the use of Quantum Defect Theory scaling laws, allows for a comprehensive analysis of the regular patterns resulting from the coupling between Rydberg series and doubly excited states. The results should open the door for more efficient quasi-diabatization of the potential energy curves which is required for calculating cross sections and rate coefficients of the (e + H 2 + ) collisional processes, involved in the plasma modeling for fusion devices.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

High-fidelity first principles nonadiabaticity: diabatization, analytic representation of global diabatic potential energy matrices, and quantum dynamics

We report nonadiabatic dynamics, which goes beyond the Born–Oppenheimer approximation, has increasingly been shown to play an important role in chemical processes, particularly those involving electronically excited states. Understanding multistate dynamics requires rigorous quantum characterization of both electronic and nuclear motion. However, such first principles treatments of multi-dimensional systems have so far been rather limited due to the lack of accurate coupled potential energy surfaces and difficulties associated with quantum dynamics. In this Perspective, we review recent advances in developing high-fidelity analytical diabatic potential energy matrices for quantum dynamical investigations of polyatomic uni- and bi-molecular nonadiabatic processes, by machine learning of high-level ab initio data. Special attention is paid to methods of diabatization, high fidelity construction of multi-state coupled potential energy surfaces and property surfaces, as well as quantum mechanical characterization of nonadiabatic nuclear dynamics. To illustrate the tremendous progress made by these new developments, several examples are discussed, in which direct comparison with quantum state resolved measurements led to either confirmation of the observation or sometimes reinterpretation of the experimental data. The insights gained in these prototypical systems greatly advance our understanding of nonadiabatic dynamics in chemical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Vibronic exciton model for low bandgap donor–acceptor polymers

In this study, a vibronic exciton model is introduced to describe the excited state band structure and associated absorption spectra of low bandgap donor–acceptor conjugated polymers. The Hamiltonian is represented in a diabatic basis consisting of Frenkel-like donor and acceptor fragment excitations as well as charge-transfer (CT) excitations between neighboring fragments. States are coupled to each other through electron and hole transfer as well as Coulombically, through interacting fragment transition dipole moments. Local vibronic coupling involving the prominent aromatic-quinoidal vibrational mode, which is responsible for pronounced vibronic progressions in most conjugated oligomers and polymers, is also included. The DAD repeat unit is shown to behave like a J-aggregate trimer, driven by both the sizable in-phase electron and hole transfer integrals between donor and acceptor fragments as well as negative Coulomb coupling between donor and acceptor fragment excitations. The J-aggregate behavior is enhanced in the polymer limit through inter-repeat unit coupling, with the 0–0 vibronic peak significantly enhanced in the lowest-energy near-IR band. In addition, the radiative rate is enhanced by the number of coherently connected repeat units. The near-IR band is shown to possess roughly equal admixtures of CT and Frenkel-like excitations. Applications are made to the polymer PffBT4T-2DT, with the simulated absorption spectrum quantitatively capturing the salient features of the measured spectrum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Enabling complete multichannel nonadiabatic dynamics: A global representation of the two-channel coupled, 1,2 1 A and 1 3 A states of NH 3 using neural networks

Global coupled three-state two-channel potential energy and property/interaction (dipole and spin–orbit coupling) surfaces for the dissociation of NH 3 (Ã) into NH + H 2 and NH 2 + H are reported. The permutational invariant polynomial-neural network approach is used to simultaneously fit and diabatize the electronic Hamiltonian by fitting the energies, energy gradients, and derivative couplings of the two coupled lowest-lying singlet states as well as fitting the energy and energy gradients of the lowest-lying triplet state. The key issue in fitting property matrix elements in the diabatic basis is that the diabatic surfaces must be smooth, that is, the diabatization must remove spikes in the original adiabatic property surfaces attributable to the switch of electronic wavefunctions at the conical intersection seam. Here, we employ the fit potential energy matrix to transform properties in the adiabatic representation to a quasi-diabatic representation and remove the discontinuity near the conical intersection seam. The property matrix elements can then be fit with smooth neural network functions. The coupled potential energy surfaces along with the dipole and spin–orbit coupling surfaces will enable more accurate and complete treatment of optical transitions, as well as nonadiabatic internal conversion and intersystem crossing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1977

Quantum mechanical theory of a structured atom-diatom collision system - A + BC/1-Sigma/

The problem of a 2-p state atom colliding with a singlet sigma state diatom, which involves multiple potential surfaces, is investigated. Within a diabatic representation for the electronic degrees of freedom (plus spin-orbit interaction), coupled scattering equations are derived in both space-fixed and body-fixed coordinate systems. Coefficients, analogous to Percival-Seaton coefficients, are obtained. Approximations to the exact equations, including angular momenta decoupling approximations, are discussed for both the space-fixed and body-fixed formalisms.

Devries, P. L.↗
NASA NTRSDate not supplied

Dissociative Recombination (DR) and Associative Ionization (AI) Cross Section Calculations for the NO+ + e yields N + O (2D+3P, 2P+3P, and 2D+1D) Reaction for Atmospheric Entry Modeling

During entry of a space craft into Earth atmosphere, the flow surrounding the vehicle becomes partially ionized leading to significant cation and free-electron production. Subsequently, electron impact excitation and dissociation form radiating excited state species that contribute to the heat load on the vehicle. While experimental data on selected total cross sections are available, few experiments address the need for accurate AI cross sections for metastable atomic states at the high temperatures realized in atmospheric re-entry. In order to maintain desired safety margins during atmospheric entry of a space vehicle, chemical reaction models need to accurately account for this process. For the present study, we have computed vibrationally resolved cross sections for the DR of NO+ for electron energies between 0.01 to 10 eV and apply microscopic reversibility to obtain the AI cross sections and rate coefficients. For the DR cross section calculations, we use state-of-the-art MRCI potential energy curves. The resulting adiabatic potential curves are transformed to a diabatic representation, which is used in time-dependent wave packet calculations to describe the nuclear motion of the dissociating cation upon collision with an electron. Based on the wave function evolution in time, these calculations provide T-matrix and cross sections for the DR including recombination into the low energy metastable atomic states. The DR and AI rate coefficients are compared with the available experimental data.

Ewa Papajak↗
NASA NTRS1995

The Dissociative Recombination of OH(+)

Theoretical quantum chemical calculations of the cross sections and rates for the dissociative recombination of the upsilon = 0 level of the ground state of OH(+) show that recombination occurs primarily along the 2 (2)Pi diabatic route. The products are 0((1)D) and a hot H atom with 6.1 eV kinetic energy. The coupling to the resonances is very small and the indirect recombination mechanism plays only a minor role. The recommended value for the rate coefficient is (6.3 +/- 0.7) x 10(exp -9)x (T(e)/1300)(exp -0.48) cu.cm/s for 10 less than T(e) less than 1000 K.

Guberman, Steven L.↗
NASA NTRS1982

Numerical simulation of the development of mean monsoon circulation in July

Eight different experiments are carried out, ranging from 8 to 20 days, with a primitive equation model consisting of five atmospheric layers and one oceanic layer. The purpose is to investigate the relative importance of radiative heating and deep cumulus condensation, orography, and initial conditions for the development of the mean monsoon circulation from June to July in the 0-180 deg E, 25 deg S - 55 deg N region. Two alternative initial states are used, one based on the observed monthly mean June pressure distribution, the other on the mean June zonal average pressure distribution. Whereas large-scale condensation and actual land and sea distributions are included in every experiment, deep cumulus cone condensation and radiative heating are always taken together. It is found that the means sea level pressure distribution and low-level flow pattern produced by these simulations are in the main determined by the diabatic heating distribution and are influenced somewhat by orography; they are, however, almost independent of the initial state. The low pressure systems are found to develop faster when diurnal variation of solar radiation is allowed for; this is thought to be due mainly to the more vigorous cumulus activity during the day.

Kuo, H. L.↗
NASA NTRS1983

Transport and the seasonal variation of ozone

The transport mechanisms responsible for the seasonal behavior of total ozone are deduced from the comparison of model results to stratospheric data. The seasonal transport is dominated by a combination of the diabatic circulation and transient planetary wave activity acting on a diffusively and photochemically determined background state. The seasonal variation is not correctly modeled as a diffusive process. The buildup of total ozone at high latitudes during winter is dependent upon transient planetary wave activity of sufficient strength to cause the breakdown of the polar vortex. While midwinter warmings are responsible for enhanced ozone transport to high latitudes, the final warming marking the transition from zonal mean westerlies to zonal mean easterlies is the most important event leading to the spring maximum. The final warming is not followed by reacceleration of the mean flow; so that the ozone transport associated with this event is more pronounced than that associated with midwinter warmings.

Rood, R. B.↗
NASA NTRS1982

Short-term climatic fluctuations forced by thermal anomalies

A two level, global, spectral model using pressure as a vertical coordinate was developed. The system of equations describing the model is nonlinear and quasi-geostrophic (linear balance). Static stability is variable in the model. A moisture budget is calculated in the lower layer only. Convective adjustment is used to avoid supercritical temperature lapse rates. The mechanical forcing of topography is introduced as a vertical velocity at the lower boundary. Solar forcing is specified assuming a daily mean zenith angle. The differential diabatic heating between land and sea is paramterized. On land and sea ice surfaces, a steady state thermal energy equation is solved to calculate the surface temperature. On the oceans, the sea surface temperature is specified as the climatological average for January. The model is used to simulate the January, February and March circulations.

Hanna, A. F.↗
NASA NTRS1984

Short-term climatic fluctuations forced by thermal anomalies

A two level, global, spectral model using pressure as a vertical coordinate was developed. The system of equations describing the model is nonlinear and quasi-geostrophic (linear balance). Static stability is variable in the model. A moisture budget is calculated in the lower layer only. Convective adjustment is used to avoid supercritical temperature lapse rates. The mechanical forcing of topography is introduced as a vertical velocity at the lower boundary. Solar forcing is specified assuming a daily mean zenith angle. The differential diabatic heating between land and sea is parameterized. On land and sea ice surfaces, a steady state thermal energy equation is solved to calculate the surface temperature. On the oceans, the sea surface temperature is specified as the climatological average for January. The model is used to simulate the January, February and March circulations. Previously announced in STAR as N83-14822

Hanna, A. F.↗
NASA NTRS1983

Short-term climatic fluctuations forced by thermal anomalies

A two level, global, spectral model using pressure as a vertical coordinate was developed. The system of equations describing the model is nonlinear and quasi-geostrophic (linear balance). Static stability is variable in the model. A moisture budget is calculated in the lower layer only. Convective adjustment is used to avoid supercritical temperature lapse rates. The mechanical forcing of topography is introduced as a vertical velocity at the lower boundary. Solar forcing is specified assuming a daily mean zenith angle. The differential diabatic heating between land and sea is parameterized. On land and sea ice surfaces, a steady state thermal energy equation is solved to calculate the surface temperature. On the oceans, the sea surface temperature is specified as the climatological average for January. The model is used to simulate the January, February and March circulations. Previously announced in STAR as N83-14822

Hanna, A. F.↗
DOE OSTI2025

Fast methods for multisite charge transfer processes. I. Constrained, state averaged CASSCF(1,n) and CASSCF(2n − 1,n) simulations

We design a dynamically weighted state-averaged constrained complete active space self-consistent field (DW-SA-cCASSCF) algorithm to treat electrons or holes moving between n molecular fragments (where n can be larger than 2). Within such a so-called eDSCn/hDSCn approach, we consider configurations that are mutually single excitations of each other, and we apply a generalized set of constraints to tailor the method for studying charge transfer problems. The constrained optimization problem is efficiently solved using a DIIS-SQP algorithm, thus maintaining computational efficiency. We demonstrate the method for a finite Su–Schrieffer–Heeger chain, successfully reproducing the expected exponential decay of diabatic couplings with distance. When combined with a gradient, the current extension immediately enables efficient nonadiabatic dynamics simulations of complex multi-state charge transfer processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Trajectory Simulations of Upper Tropospheric Humidity

We present comparisons of simulations of upper tropospheric humidity at 215 and 146 hPa with satellite measurements. Our model uses diabatic trajectories to advect water vapor from an initial condition of 100% relative humidity to the final state. The model does not allow parcels' relative humidity to exceed 100%, and in this way crudely incorporates condensation. We find that this simple model does a good job of simulating the observations. Sensitivity studies suggest that one must have realistic wind velocities in order to accurately simulate the humidity distribution; microphysical parameterizations seem to be less important. Comparisions between simulations using UKMO and NCEP horizontal winds will be discussed.

Dessler, A. E.↗
DOE OSTI2023

Modeling fission dynamics at the barrier in a discrete-basis formalism

A configuration-interaction model is presented for the barrier region of induced fission. The configuration space is composed of seniority-zero configurations constructed from self-consistent mean-field wave functions. The Hamiltonian matrix elements between configurations include diabatic and pairing interactions between particles. Other aspects of the Hamiltonian are treated statistically, guided by phenomenological input of compound-nucleus transmission coefficients. In this exploratory study the configuration space is restricted to neutron excitations only. A key observable calculated in the model is the fission-to-capture branching ratio. We find that both pairing and diabatic interactions are important for achieving large branching to the fission channels. In accordance with the transition-state theory of fission, the calculated branching ratio is found to be quite insensitive to the fission decay widths of the pre-scission configurations. Furthermore, the barrier-top dynamics appear to be quite different from transition-state theory in that the transport is distributed over many excited configurations at the barrier top.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗