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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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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
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 OSTI2022

Diabatic Valence-Hole States in the C 2 Molecule: “Putting Humpty Dumpty Together Again”

Despite the long history of spectroscopic studies of the C$_2$ molecule, fundamental questions about its chemical bonding are still being hotly debated. The complex electronic structure of C$_2$ is a consequence of its dense manifold of near-degenerate, low-lying electronic states. A global multi-state diabatic model is proposed here to disentangle the numerous configuration interactions within four symmetry manifolds of C$_2$ ($^{1}\Pi_g$, $^{3}\Pi_g$, $^{1}\Sigma_u^+$, and $^{3}\Sigma_u^+$). The key concept of our model is the existence of two "valence-hole" configurations, $2\sigma_g^22\sigma_u^11\pi_{u}^33\sigma_g^2$ for $^{1,3}\Pi_g$ states and $2\sigma_g^22\sigma_u^11\pi_{u}^43\sigma_g^1$ for $^{1,3}\Sigma_u^+$ states that derive from $3\sigma_g\leftarrow2\sigma_u$ electron promotion. The lowest-energy state from each of the four C$_2$ symmetry species is dominated by this type of valence-hole configuration at its equilibrium internuclear separation. Finally, as a result of their large binding energy (nominal bond order of 3) and correlation with the 2s$^2$2p$^2$+2s2p$^3$ separated-atom configurations, the presence of these valence-hole configurations has a profound impact on the $global$ electronic structure and unimolecular dynamics of C$_2$.

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

On the nonadiabatic collisional quenching of OH(A) by H 2 : a four coupled quasi-diabatic state description

A four-state diabatic potential energy matrix (DPEM), H d , for the description of the nonadiabatic quenching of OH(A 2 Σ + ) by collisions with H 2 is reported. The DPEM is constructed as a fit to adiabatic energies, energy gradients, and derivative couplings obtained exclusively from multireference configuration interaction wave functions. A four-adiabatic-electronic-state representation is used in order to describe all energetically accessible regions of the nuclear coordinate space. Partial permutation-inversion symmetry is incorporated into the representation. Here, the fit is based on electronic structure data at 42 882 points, described by over 1.6 million least squares equations with a root mean square (mean unsigned) error of 178(83) cm –1 . Comparison of ab initio and H d determined minima, saddle points, and energy minimized points on C 2v , C s , C ∞v , and C 1 (noncoplanar) portions of two conical intersection seams are used to establish the accuracy of the H d .

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Diabatic Hamiltonian matrix elements made simple

With a view to applying the generator coordinate method to large configuration spaces, we propose a simple approximate formula to compute diabatic many-body matrix elements without having to evaluate two-body interaction matrix elements. Here, the method is illustrated with two analytically solvable Hamiltonians based on the harmonic oscillator.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS1984

Analysis of Diabatic Heating During FGGE

The objective is to examine the maintenance of momentum and thermal fields in the Southern Hemisphere and the diabatic heating and generation of available potential energy of the entire global atmosphere. The data generated by the Goddard Laboratory for Atmospheric Sciences First GARP Global Experiment (FGGE) III-b analysis for SOP1 and SOP2 are used for this effort. It is observed that the atmospheric circulation of the Southern Hemisphere exhibits a double jet structure (subtropical jet and polar jet) in winter and a single jet in summer during the FGGE year. The geographic distribution of standard deviation in the height field at 500 mb indicates that the major eddy activities occur in the downstream side of the polar jet and poleward side of the subtropic jet in winter. However, the major eddy activites go hand-in-hand with the jet stream in summer. The momentum transport is essentially carried out by the transient eddies in both seasons. The distribution of the temperature field is more axisymmetric in the Southern Hemisphere than in the Northern Hemisphere. The sensible heat is mainly transported poleward by transient eddies along the strong baroclinic zone where the jet streams are located. In other seasons, it is shown from the geographic distribution of the divergence of transient eddy sensible heat flux that the Antarctic continent acts as a heat sink to consume the sensible heat converged toward the polar area from the middle and low latitudes.

Chen, T. C.↗
NASA NTRS1986

Tracer transport by the diabatic circulation deduced from satellite observations

Nimbus-7 sensor data were used to track the diabatic circulation in the stratosphere to study the advective transport of CH4 and N2O as tracer species. Advective transport by the mean circulation was found to be a function of the temperature field and associated deviations from radiative equilibrium. A photochemical model was applied to account for the disappearance of the tracer species from the stratosphere. Comparisons between the SAMS data and modeling on the basis of the chemical loss rates of the tracers and the LIMS circulation data showed that the model predictions underestimated the resident abundances, although the global distributions and circulations exhibited a good match.

Solomon, S.↗
NASA NTRS1988

Diabatic initialization for a mesoscale model simulation experiment

A mesoscale model simulation of a 'surrogate' atmosphere designed for the evaluation of adiabatic initialization and moisture enhancement techniques is briefly described. The simulation provides mesoscale precipitation rates and associated diabatic heating fields which are known exactly and are internally consistent within the context of the model. The advantage of this approach is that a numerical model can easily serve as a source of mesoscale data in the usual absence of internally consistent mesoscale observed data sets.

Kalb, Michael W.↗
NASA NTRS1989

Global distribution of moisture, evaporation-precipitation, and diabatic heating rates

Global archives were established for ECMWF 12-hour, multilevel analysis beginning 1 January 1985; day and night IR temperatures, and solar incoming and solar absorbed. Routines were written to access these data conveniently from NASA/MSFC MASSTOR facility for diagnostic analysis. Calculations of diabatic heating rates were performed from the ECMWF data using 4-day intervals. Calculations of precipitable water (W) from 1 May 1985 were carried out using the ECMWF data. Because a major operational change on 1 May 1985 had a significant impact on the moisture field, values prior to that date are incompatible with subsequent analyses.

Christy, John R.↗
NASA NTRS1989

Evidence for diabatic cooling and poleward transport within and around the 1987 Antarctic ozone hole

Atmospheric dynamics at altitudes of 17.5-19 km were analyzed using measurements of N2O, total water, total odd-nitrogen species, and potential vorticity (derived from pressures, temperatures, and wind speeds) obtained aboard the ER-2 aircraft flown in the period between August 23 and September 22 during the Airborne Antarctic Ozone Experiment. Results indicated a consistent gradual poleward movement of air, extending from about 10 deg in latitude outside the boundary of the ozone hole to about 5 deg inside. Evidence is presented of ongoing diabatic cooling throughout this zone, both inside and outside the chemically perturbed region.

Profitt, M. H.↗
NASA NTRS1989

The role of diabatic heating in maintaining the upper-tropospheric baroclinic zone in the South Pacific

The four-dimensional structure of the region in the South Pacific convergence zone (SPCZ) during January 10-18, 1979 is studied using a modified set of ECMWF FGGE level III-b analyses. The effects of kinematic and thermodynamic processes on maintaining the upper baroclinic region corresponding with the subtropical jet are analyzed. The role of adiabatic and diabatic processes in the maintenance of baroclinicity in the area of the SPCZ is examined using the frontogenetical function. It is observed that the processes affecting the evolution of baroclinicity in the SPCZ region differ from those in the middle latitude; possible reasons for these differences are proposed.

Robertson, Franklin R.↗
NASA NTRS1990

Global-scale, intraseasonal fluctuations of diabatic forcing of the atmosphere

Fields of diabatic heating rate estimates (H) for 5-day periods were calculated from the European Center for Medium Weather Forecasts (ECMWF) analyses since 1985 as the residual of the dry thermodynamic equation. Included in these fields are the horizontal and vertical divergences of heat for both mean and eddy statistics. Previous work dealt with 4-day periods, however, with the emphasis in the Global Precipitation Climatology Project (GPCP) for 5-day period totals the change was made to accommodate the GPCP product. H has long been associated with cold tropical cloud-top temperatures as measured by polar orbiting outgoing longwave radiation (OLR) sensors. Correlations between H and OLR fields on three time scales indicate a moderate amount of agreement. For periods less than 90 days, significant negative correlations are found between H and OLR for (1) tropical and NH midlatitude oceanic areas, and (2) for zonal and hemispheric mean values. Positive correlations are seen in NH mean and continental areas of N. Africa, N. America, N. Asia and Antarctica. These latter results reflect seasonal heating and cooling. Comparisons have been made between H as H as calculated from the ECMWF analyses and output from the CCM1 T42 simulations. The CCM1 tends to have a more cellular structure with more heating (precipitation) over land versus that observed (ECMWF) over oceans.

Christy, John R.↗
NASA NTRS1991

Research on diabatic initialization

The objective was to contribute to the improvement of the analyses of irrotational wind and moisture fields in the trophics through advancement in the technique of initialization by incorporating diabatic effects. Significant accomplishments made during the period May 1990 to April 1991 in the following areas are presented: (1) estimation of the uncertainty of daily synoptic analyses in the tropics; (2) normal modes of Laplace's tidal equations for zonal wavenumber zero; and (3) tropical initialization to ameliorate the spin-up problem of precipitation forecasts. The focus of current research and plans for next year are also presented.

Kasahara, Akira↗
NASA NTRS1991

Diabatic heating rate estimates from European Centre for Medium-Range Weather Forecasts analyses

Vertically integrated diabatic heating rate estimates (H) calculated from 32 months of European Center for Medium-Range Weather Forecasts daily analyses (May 1985-December 1987) are determined as residuals of the thermodynamic equation in pressure coordinates. Values for global, hemispheric, zonal, and grid point H are given as they vary over the time period examined. The distribution of H is compared with previous results and with outgoing longwave radiation (OLR) measurements. The most significant negative correlations between H and OLR occur for (1) tropical and Northern-Hemisphere mid-latitude oceanic areas and (2) zonal and hemispheric mean values for periods less than 90 days. Largest positive correlations are seen in periods greater than 90 days for the Northern Hemispheric mean and continental areas of North Africa, North America, northern Asia, and Antarctica. The physical basis for these relationships is discussed. An interyear comparison between 1986 and 1987 reveals the ENSO signal.

Christy, John R.↗
NASA NTRS1991

Effects of radiation and turbulence on the diabatic heating and water budget of the stratiform region of a tropical cloud cluster

A twi-dimensional kinematic model has been used to diagnose the thermodynamic, water vapor, and hydrometeor fields of the stratiform clouds associated with a mesoscale tropical cloud cluster. The model incorporates ice- and water-cloud microphysics, visible and infrared radiation, and convective adjustment. It is intended to determine the relative contributions of radiation, mycrophysics, and turbulence to diabatic heating, and the effects that radiation has on the water budget of the cluster in the absence of dynamical interactions. The model has been initialized with thermodynamic fields and wind velocities diagnosed from a GATE tropical squall line. It is found that radiation does not directly affect the water budget of the stratiform region, and any radiative effect on hydrometeors must involve interaction with dynamics.

Churchill, Dean D.↗
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↗