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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Climate Forcing and Trends of Organic Aerosols in the Community Earth System Model (CESM2)

The Community Earth System Model version 2 (CESM2) includes three main atmospheric configurations: the Community Atmosphere Model version 6 (CAM6) with simplified chemistry and a simplified organic aerosol (OA) scheme, CAM6 with comprehensive tropospheric and stratospheric chemistry representation (CAM6-chem), and the Whole Atmosphere Community Climate Model version 6 (WACCM6). Both, CAM6-chem and WACCM6 include a more comprehensive secondary organic aerosols (SOA) approach using the volatility basis set (vbs) scheme and prognostic stratospheric aerosols. This paper describes the different OA schemes available in the different atmospheric configurations of CESM2 and discusses differences in aerosol burden and resulting climate forcings. Derived OA burden and trends differ due to differences in OA formation using the different approaches. Regional differences in Aerosol Optical Depth with larger values using the comprehensive approach occur over SOA source regions. Stronger increasing SOA trends between 1960 and 2015 in WACCM6 compared to CAM6 are due to increasing biogenic emissions aligned with increasing surface temperatures. Using the comprehensive SOA approach further leads to improved comparisons to aircraft observations and SOA formation of ˜143 Tg/yr. We further use WACCM6 to identify source contributions of OA from biogenic, fossil fuel, and biomass burning emissions, to quantify SOA amounts and trends from these sources. Increasing SOA trends between 1960 and 2015 are the result of increasing biogenic emissions aligned with increasing surface temperatures. Biogenic emissions are at least two thirds of the total SOA burden. In addition, SOA source contributions from fossil fuel emissions become more important, with largest values over Southeast Asia. The estimated total anthropogenic forcing of OA in WACCM6 for 1995–2010 conditions is -0.43 W/m2, mostly from the aerosol direct effect.

Tilmes, S↗
DOE OSTI2022

Airborne Lidar Measurements of XCO 2 in Synoptically Active Environment and Associated Comparisons With Numerical Simulations

Frontal boundaries have been shown to cause large changes in CO 2 mole-fractions, but clouds and the complex vertical structure of fronts make these gradients difficult to observe. It remains unclear how the column average CO 2 dry air mole-fraction (XCO 2 ) changes spatially across fronts, and how well airborne lidar observations, data assimilation systems, and numerical models without assimilation capture XCO 2 frontal contrasts (ΔXCO 2 , i.e., warm minus cold sector average of XCO 2 ). We demonstrated the potential of airborne Multifunctional Fiber Laser Lidar (MFLL) measurements in heterogeneous weather conditions (i.e., frontal environment) to investigate the ΔXCO 2 during four seasonal field campaigns of the Atmospheric Carbon and Transport-America (ACT-America) mission. Most frontal cases in summer (winter) reveal higher (lower) XCO 2 in the warm (cold) sector than in the cold (warm) sector. During the transitional seasons (spring and fall), no clear signal in ΔXCO 2 was observed. Intercomparison among the MFLL, assimilated fields from NASA's Global Modeling and Assimilation Office (GMAO), and simulations from the Weather Research and Forecasting-—Chemistry (WRF-Chem) showed that (a) all products had a similar sign of ΔXCO 2 though with different levels of agreement in ΔXCO 2 magnitudes among seasons; (b) ΔXCO 2 in summer decreases with altitude; and (c) significant challenges remain in observing and simulating XCO 2 frontal contrasts. A linear regression analyses between ΔXCO 2 for MFLL versus GMAO, and MFLL versus WRF-Chem for summer-2016 cases yielded a correlation coefficient of 0.95 and 0.88, respectively. The reported ΔXCO 2 variability among four seasons provide guidance to the spatial structures of XCO 2 transport errors in models and satellite measurements of XCO 2 in synoptically-active weather systems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Modeling Isoprene Emission Response to Drought and Heatwaves Within MEGAN Using Evapotranspiration Data and by Coupling With the Community Land Model

We introduce two new drought stress algorithms designed to simulate isoprene emission with the Model of Emissions of Gases and Aerosols from Nature (MEGAN) model. The two approaches include the representation of the impact of drought on isoprene emission with a simple empirical approach for offline MEGAN applications and a more process-based approach for online MEGAN in Community Land Model (CLM) simulations. The two versions differ in their implementation of leaf-temperature impacts of mild drought. For the online version of MEGAN that is coupled to CLM, the impact of drought on leaf temperature is simulated directly and the calculated leaf temperature is considered for the estimation of isoprene emission. For the offline version, we apply an empirical algorithm derived from whole-canopy flux measurements for simulating the impact of drought ranging from mild to severe stage. In addition, the offline approach adopts the ratio ($f$ PET ) of actual evapotranspiration to potential evapotranspiration to quantify the severity of drought instead of using soil moisture. We applied the two algorithms in the CLM-CAM-chem (the Community Atmosphere Model with Chemistry) model to simulate the impact of drought on isoprene emission and found that drought can decrease isoprene emission globally by 11% in 2012. We further compared the formaldehyde (HCHO) vertical column density simulated by CAM-chem to satellite HCHO observations. We found that the proposed drought algorithm can improve the match with the HCHO observations during droughts, but the performance of the drought algorithm is limited by the capacity of the model to capture the severity of drought.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Effects of Pollen on Hydrometeors and Precipitation in a Convective System

Anemophilous (wind-driven) pollen is one type of primary biological aerosol particle, which can rupture under high humidity conditions and form smaller sub-pollen particles (SPPs). Both pollen and SPPs can reach the upper troposphere under convective conditions, acting as cloud condensation nuclei (CCN) and ice nucleating particles (INPs), thus influencing cloud formation and precipitation. However, the impacts of these biological aerosols on cold cloud formation and local climate remain unclear as there are large uncertainties on their emission flux and ice nucleating abilities. Here, we incorporate pollen emission and rupture processes in the Weather Research and Forecasting Model with Chemistry (WRF-Chem) simulations and update the Morrison microphysics scheme within WRF-Chem using aerosol-aware INP parameterizations to account for pollen in addition to other anthropogenic and biogenic aerosol. INP parameterizations for pollen and SPP are derived from laboratory experiments. When including pollen rupture rates as observed in a series of chamber studies, SPP concentrations increase, leading to an increase of cloud ice and water by up to 50% and potentially extending the duration of the convective system. Among all simulated hydrometeors, graupel and raindrops exhibit the largest enhancements from the inclusion of SPPs, with intensifying precipitation at the backside of the convective system and a greater spatial extent. Sensitivity simulations indicate that SPPs have a greater effect on cloud microphysical processes than whole pollen grains, and further observational evidence is needed to constrain these processes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Identification of the acetaldehyde oxide Criegee intermediate reaction network in the ozone-assisted low-temperature oxidation of trans -2-butene

Uni- and bi-molecular reactions involving Criegee intermediates (CIs) have been the focus of many studies due to the role these molecules play in atmospheric chemistry. The reactivity of CIs is known to strongly depend on their structure. The reaction network of the second simplest CI, acetaldehyde oxide (CH 3 CHOO), is investigated in this work in an atmospheric pressure jet-stirred reactor (JSR) during the ozonolysis of trans-2-butene to explore the kinetic pathways relevant to atmospheric chemistry and low-temperature combustion. The mole fraction profiles of reactants, intermediates, and final products are determined by means of molecular-beam mass spectrometry in conjunction with single-photon ionization employing tunable synchrotron-generated vacuum ultraviolet radiation. A network of CI reactions is identified in the temperature region below 600 K, characterized by CI addition to trans-2-butene, water, formaldehyde, formic acid, and methanol. No sequential additions of the CH 3 CHOO CI are observed, in contrast with the reactivity of the simplest CI (H 2 COO) and the earlier observation of an extensive reaction network with up to four H 2 COO sequential additions (Phys. Chem. Chem. Phys., 2019, 21, 7341–7357). Experimental photoionization efficiency scans recorded at 300 K and 425 K and ab initio threshold energy calculations lead to the identification and quantification of previously elusive intermediates, such as ketohydroperoxide and hydroperoxide species. Specifically, the C 4 H 8 + O 3 adduct is identified as a ketohydroperoxide (KHP, 3-hydroperoxybutan-2-one, CH 3 C([double bond, length as m-dash]O)CH(CH 3 )OOH), while hydroxyacetaldehyde (glycolaldehyde, HCOCH 2 OH) formation is attributed to unimolecular isomerization of the CIs. Other hydroperoxide species such as methyl hydroperoxide (CH 3 OOH), ethyl hydroperoxide (C 2 H 5 OOH), butyl hydroperoxide (OOH), hydroperoxyl acetaldehyde (HOOCH 2 CHO), hydroxyethyl hydroperoxide (CH 3 CH(OH)OOH), but-1-enyl-3-hydroperoxide, and 4-hydroxy-3-methylpentan-2-one (HOCH(CH 3 )CH(CH 3 )C([double bond, length as m-dash]O)CH 3 ) are also identified. Detection of additional oxygenated species such as methanol, ethanol, ketene, and aldehydes suggests multiple active oxidation routes. Finally, these results provide additional evidence that CIs are key intermediates of the ozone-unsaturated hydrocarbon reactions providing critical inputs for improved kinetics models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Thermal and concentration effects on 1 H NMR relaxation of Gd 3+ -aqua using MD simulations and measurements

We report gadolinium-based contrast agents are key in clinical MRI for enhancing the longitudinal NMR relativity (r 1 ) of hydrogen nuclei ( 1 H) in water and improving the contrast among different tissues. The importance of MRI in clinical practice cannot be gainsaid, yet the interpretation of MRI relies on models with severe assumptions, reflecting a poor understanding of the molecular-scale relaxation processes. In a step towards building a clearer understanding of the relaxation processes, here we investigate thermal and concentration effects on r 1 of the Gd 3+ -aqua complex using both semi-classical molecular dynamics (MD) simulations and measurements. We follow the MD simulation approach recently introduced by [Singer et al., Phys. Chem. Chem. Phys., 2021, 23, 20974], in which no NMR relaxation model or free-parameter is assumed to predict r 1 , thereby bringing new insights into the physics of r 1 on a molecular scale. We expand the autocorrelation function G(t) in terms of molecular modes and determine the thermal activation energies of the two largest modes, both of which are consistent with the range of literature values for rotational diffusion. We also determine the activation energies for translational diffusion and low-field electron-spin relaxation, both of which are consistent with the literature. Furthermore, we validate the MD simulations at human body temperature and concentrations of the paramagnetic ion used in clinical MRI, and we quantify the uncertainties in both simulations and measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Correction: Impact of lanthanide ion complexation and temperature on the chemical reactivity of N , N , N ′, N ′-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation

Correction for ‘Impact of lanthanide ion complexation and temperature on the chemical reactivity of N , N , N ′, N ′-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation’ by Gregory P. Horne et al. , Phys. Chem. Chem. Phys. , 2023, 25 , 16404–16413, https://doi.org/10.1039/D3CP01119D.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Time-resolved momentum imaging of UV photodynamics in structural isomers of iodopropane probed by site-selective XUV ionization

The photodynamics of 1- and 2-iodopropane (1 and 2-IP) were studied in a time-resolved scheme incorporating ultraviolet (UV) excitation and extreme ultraviolet (XUV) probing, which initiates photoionization selectively from the I 4d core orbital. UV absorption in the A-band of both isomers leads to prompt C–I bond fission, with significant disposal of internal energy into the propyl radical product. Site-selective ionization enables a range of charge transfer (CT) processes between the nascent highly charged iodine ions and neutral propyl radicals, dependent on the interfragment distance at the instant of ionization. Subtle differences in the dynamics of these CT processes between the two isomers are observed. In 1-IP, the kinetic energies of iodine ions produced by UV photodissociation and subsequent XUV multiple ionization increased notably over the first few hundred femtoseconds, which could be understood in terms of differing gradients along the photodissociation coordinates of the neutral and polycationic states involved in the pump and probe steps, respectively. Led by a recent report of HI elimination in UV photoexcited 2-IP [Todt et al., Phys. Chem. Chem. Phys., 22(46), 27338 (2020)], we also model the most likely signatures of this process in the present experiment, and can identify signal in the 2-IP data (that is absent or significantly weaker in the data from the unbranched 1-IP isomer) that is consistent with such a process occurring on ultrafast timescales.

Allum, Felix [Deutsches Elektronen-Synchrotron (DE↗
DOE OSTI2021

A generalized class of strongly stable and dimension-free T-RPMD integrators

Here, recent work shows that strong stability and dimensionality freedom are essential for robust numerical integration of thermostatted ringpolymer molecular dynamics (T-RPMD) and path-integral molecular dynamics, without which standard integrators exhibit non-ergodicity and other pathologies [R. Korol et al., J. Chem. Phys. 151, 124103 (2019) and R. Korol et al., J. Chem. Phys. 152, 104102 (2020)]. In particular, the BCOCB scheme, obtained via Cayley modification of the standard BAOAB scheme, features a simple reparametrization of the free ring-polymer sub-step that confers strong stability and dimensionality freedom and has been shown to yield excellent numerical accuracy in condensed-phase systems with large time steps. Here, we introduce a broader class of T-RPMD numerical integrators that exhibit strong stability and dimensionality freedom, irrespective of the Ornstein–Uhlenbeck friction schedule. In addition to considering equilibrium accuracy and time step stability as in previous work, we evaluate the integrators on the basis of their rates of convergence to equilibrium and their efficiency at evaluating equilibrium expectation values. Within the generalized class, we find BCOCB to be superior with respect to accuracy and efficiency for various configuration-dependent observables, although other integrators within the generalized class perform better for velocity-dependent quantities. Extensive numerical evidence indicates that the stated performance guarantees hold for the strongly anharmonic case of liquid water. Both analytical and numerical results indicate that BCOCB excels over other known integrators in terms of accuracy, efficiency, and stability with respect to time step for practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Automatic derivation of many-body theories based on general Fermi vacua

This paper describes Wick&D, an implementation of the algebra of second-quantized operators normal ordered with respect to general correlated references and the corresponding Wick theorem [D. Mukherjee, Chem. Phys. Lett. 274, 561 (1997) and W. Kutzelnigg and D. Mukherjee, J. Chem. Phys. 107, 432 (1997)]. Wick&D employs a compact representation of operators and a backtracking algorithm to efficiently evaluate Wick contractions. Since Wick&D can handle both fully and partially contracted terms, it can be applied to both projective and Fock-space many-body formalisms. To demonstrate the usefulness of Wick&D, here we use it to evaluate the single-reference coupled cluster equations up to octuple excitations and report an automated derivation and implementation of the second-order driven similarity renormalization group multireference perturbation theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗