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Parameterizing mesoscale and large-scale ice clouds in general circulation models

The paper discusses GCM parameterizations for two types of ice clouds: (1) ice clouds formed by large-scale lifting, often of limited vertical extent but usually of large-scale horizontal extent; and (2) ice clouds formed as anvils in convective systems, often of moderate vertical extent but of mesoscale size horizontally. It is shown that the former type of clouds can be parameterized with reference to an equilibrium between ice generation by deposition from vapor, and ice removal by crystal settling. The same mechanisms operate in the mesoscale clouds, but the ice content in these cases is considered to be more closely linked to the moisture supplied to the anvil by cumulus towers. It is shown that a GCM can simulate widespread ice clouds of both types.

Donner, Leo J.↗

Search for electroweak production of vector-like leptons in $\tau$-lepton and b-jet final states in pp collisions at $\sqrt{s}$ = 13 TeV with the ATLAS detector

A search for pair-production of vector-like leptons is presented, considering their decays into a third-generation Standard Model (SM) quark and a vector leptoquark ( U 1 ) as predicted by an ultraviolet-complete extension of the SM, referred to as the ‘4321’ model. Given the assumed decay of U 1 into third-generation SM fermions, the final state can contain multiple τ-leptons and b-quarks. This search is based on a dataset of pp collisions at $\sqrt{s}=13$ TeV recorded with the ATLAS detector during Run 2 of the Large Hadron Collider, corresponding to an integrated luminosity of up to $140~\textrm{fb}^{-1}$. No significant excess above the SM background prediction is observed, and 95% confidence level limits on the cross-section times branching ratio are derived as a function of the vector-like lepton mass. A lower observed (expected) limit of 910 GeV (970 GeV) is set on the vector-like lepton mass. Additionally, the results are interpreted for a supersymmetric model with an R-parity violating coupling to the third-generation quarks and leptons. Lower observed (expected) limits are obtained on the higgsino mass at 880 GeV (940 GeV) and on the wino mass at 1170 GeV (1170 GeV).

Aad, G. [CPPM, Aix-Marseille Université, CNRS/IN2P↗

SubDyn User's Guide and Theory Manual

SubDyn is a time-domain structural-dynamics module for multimember fixed-bottom substructures created by the National Renewable Energy Laboratory (NREL) through U.S. Department of Energy Wind and Water Power Program support. The module has been coupled into the FAST aero-hydro-servo-elastic computer-aided engineering (CAE) tool. Substructure types supported by SubDyn include monopiles, tripods, jackets, and other lattice-type substructures common for offshore wind installations in shallow and transitional water depths. SubDyn can also be used to model lattice support structures for land-based wind turbines. This document is organized as follows. Section 1 details how to obtain the SubDyn and FAST software archives and run both the stand-alone SubDyn or SubDyn coupled to FAST. Section 2 describes the SubDyn input files. Section 3 discusses the output files generated by SubDyn; these include echo files, a summary file, and the results file. Section 4 provides modeling guidance when using SubDyn. The SubDyn theory is covered in Section 5. Section 6 outlines future work, and Section 7 contains a list of references. Example input files are shown in Appendixes A and B. A summary of available output channels are found in Appendix C. Instructions for compiling the stand-alone SubDyn program are detailed in Appendix D. Appendix E tracks the major changes we have made to SubDyn for each public release.

17 WIND ENERGY↗

Interpreting T-History Data on Supercooling and Phase Change Enthalpy of a Salt-Hydrogel Complex for Building Thermal Management

Phase change materials (PCMs) are promising materials for storing and discharging latent heat in buildings to regulate the thermal environment. Measurement of salt hydrate PCM thermal performance is often challenging because of supercooling and phase segregation. Though differential scanning calorimetry (DSC) has been widely used to measure thermal properties of various phase change materials, DSC uses milligrams of sample and is unrealistic for predicting large-scale materials performance. The T-history method [1], in contrast, handles higher volumes but the analysis typically requires a lumped capacitance assumption. Here, we report and analyze T-History data on a novel salt-hydrogel complex with high viscosity, that renders low Biot number sample preparation extremely challenging. We re-examine the standard T-history method and compared against DSC data in this complex material. We report details of an experimental setup, built with necessary additions to a controlled environmental chamber. We carefully examine the validity of the lumped capacitance assumption and suggest a modified analysis using a computational approach for reliable data. Experimental parameters such as ramp rate and temperature range of the environmental chamber are considered via computational modeling to understand the effect of ramp rate on supercooling [2]. Finally, we report thermal cycling experiments on the salt-hydrogel complex. Our modified approach to measuring supercooling and enthalpy of fusion at large scales is important in better understanding the performance of phase-change materials at scale for building thermal storage. References: [1] Marin, Jose M, Belen Zalba, Luisa F Cabeza, and Harald Mehling. “Determination of Enthalpy Temperature Curves of Phase Change Materials with the Temperature-History Method: Improvement to Temperature Dependent Properties.” Measurement Science and Technology 14, no. 2 (February 1, 2003): 184–89. https://doi.org/10.1088/0957-0233/14/2/305. [2] Safari, A., R. Saidur, F.A. Sulaiman, Yan Xu, and Joe Dong. “A Review on Supercooling of Phase Change Materials in Thermal Energy Storage Systems.” Renewable and Sustainable Energy Reviews 70 (April 2017): 905–19. https://doi.org/10.1016/j.rser.2016.11.272

thermodynamics↗

Satellite power system (SPS) magnetron tube assessment study

Taks performed to extend the data base and to define a technology development program for the magnetron directional amplifier for the SPS are reviewed. These include: (1) demonstrating the tracking of phase and amplitude of the microwave output to phase and amplitude references; (2) expanding the range of power over which the directional amplifier will operate; (3)recognizing the importance of amplitude control in overall system design and in simplifying power conditioning; (4) developing a preliminary design for the overall architecture of the power module; (5) demonstrating magnetron starting using the amplitude control system; (6) mathematically modelling and performing a computerized study of the pyrolytic graphite radiating fin; (7) defining the mass of the magnetic circuit for the SPS tube; (8) noise measurement; (9) achieving harmonic suppression by notch reflection filters; (10) estimating the mass of the transmitting antenna; (11) developing a magnetron package with power generation, phase control, and power condition functions; and (12) projecting magnetron package characteristics.

Source record↗

The Z3 model of Saturn's magnetic field and the Pioneer 11 vector helium magnetometer observations

Magnetic field observations obtained by the Pioneer 11 vector helium magnetometer are compared with the Z(sub 3) model magnetic field. These Pioneer 11 observations, obtained at close-in radial distances, constitute an important and independent test of the Z(sub 3) zonal harmonic model, which was derived from Voyager 1 and Voyager 2 fluxgate magnetometer observations. Differences between the Pioneer 11 magnetometer and the Z(sub 3) model field are found to be small (approximately 1 percent) and quantitatively consistent with the expected instrumental accuracy. A detailed examination of these differences in spacecraft payload coordinates shows that they are uniquely associated with the instrument frame of reference and operation. A much improved fit to the Pioneer 11 observations is obtained by rotation of the instrument coordinate system about the spacecraft spin axis by 1.4 degree. With this adjustment, possibly associated with an instrumental phase lag or roll attitude error, the Pioneer 11 vector helium magnetometer observations are fully consistent with the Voyager Z(sub 3) model.

Connerney, J. E. P.↗

X-Ray Spectrum of a Narrow-Line QSO

During the reporting period, seven papers using ASCA data, supported in whole or in part by this grant, were published or submitted to refereed journals. Their abstracts are given in this report, and the complete bibliographic references are listed in the Appendix. Titles include (1) A Broad-Band X-ray Study of the Geminga Pulsar; (2) ASCA Observations of PSR 1920+10 and PSR 0950+08; (3) X-ray and Optical Spectroscopy of IRAS 20181-2244: Not a Type 2 QSO, but a I Zw I Object; (4) Models for X-ray Emission from Isolated Pulsars; (5) Optical and X-ray Spectroscopy of 1E 0449.4-1823: Demise of the Original Type 2 QSO; (6) The ASCA Spectrum of the Broad-Line Radio Galaxy Pictor A: A Simple Power Law with No Fe Ka Line; and (7) ASCA Spectra of NGC 4388 and ESO 103-G35: Absorption, Reflection, and Variability in Intermediate Type Seyfert Galaxies.

Halpern, Jules P.↗

Climate and the Global Famine of 1876-78

From 1875 to 1878, concurrent multiyear droughts in Asia, Brazil, and Africa, referred to as the Great Drought, caused widespread crop failures, catalyzing the so-called Global Famine, which had fatalities exceeding 50 million people and long-lasting societal consequences. Observations, paleoclimate reconstructions, and climate model simulations are used 1) to demonstrate the severity and characterize the evolution of drought across different regions, and 2) to investigate the underlying mechanisms driving its multiyear persistence. Severe or record-setting droughts occurred on continents in both hemispheres and in multiple seasons, with the "Monsoon Asia" region being the hardest hit, experiencing the single most intense and the second most expansive drought in the last 800 years. The extreme severity, duration, and extent of this global event is associated with an extraordinary combination of preceding cool tropical Pacific conditions (1870-76), a record-breaking El Nino (1877-78), a record strong Indian Ocean dipole (1877), and record warm North Atlantic Ocean (1878) conditions. Composites of historical analogs and two sets of ensemble simulations - one forced with global sea surface temperatures (SSTs) and another forced with tropical Pacific SST - were used to distinguish the role of the extreme conditions in different ocean basins. While the drought in most regions was largely driven by the tropical Pacific SST conditions, an extreme positive phase of the Indian Ocean dipole and warm North Atlantic SSTs, both likely aided by the strong El Nino in 1877-78, intensified and prolonged droughts in Australia and Brazil, respectively, and extended the impact to northern and southeastern Africa. Climatic conditions that caused the Great Drought and Global Famine arose from natural variability, and their recurrence, with hydrological impacts intensified by global warming, could again potentially undermine global food security.

multi-year drought↗

Preliminary Medical Risk Estimates and Clinical Capability Needs for Artemis IV

BACKGROUND Human exploration spaceflight missions to the Moon and Mars present unprecedented challenges for in- mission medical care. Compared with the ISS, the greater distance from Earth will mean increased mission durations, communication delays, limited to no resupply opportunities, and significant limitations on the evacuation of ill or injured crew. Spacecraft mass, volume, and power will be curtailed while higher demands will be placed on the crew’s knowledge, skills, and abilities. In this higher risk environment, it is important to: a) quantitatively estimate human system risk attributable to medical conditions, a process known as Probabilistic Risk Analysis, and b) use these estimates to inform medical system design. IMPACT (Informing Mission Planning via Analysis of Complex Tradespaces) is a PRA and medical trade space analysis tool developed by NASA to advance exploration mission medical system design. IMPACT v1.0 improves upon and will soon replace NASA’s existing tool, the Integrated Medical Model, with: a novel evidence base baselined to exploration environments; an expanded list of 119 medical conditions; a significant increase in the number of medical resources that can be utilized and in the flexibility of their use; and the modelling of time lost performing mission-specific tasks due to medical conditions. METHODOLOGY: This abstract will present IMPACT estimates of medical system risk and clinical capability needs for the Artemis IV mission. Artemis IV is currently scheduled for 2026 and will visit the Gateway space station in lunar orbit prior to the second lunar landing of the Artemis program. The baseline Artemis IV mission that was modeled was 28 days in duration with phases including Orion outbound, 4 days on the Gateway space station in lunar orbit, 2 crew on the surface of the Moon for approximately one week, an additional 5 days on Gateway, and then return to Earth. This baseline was compared to two alternative 34-day design reference missions (DRMs) that shifted the lunar sortie earlier or later in the mission profile. Assumptions included 2 female and 2 male crew and a notional medical system mass of 25 kg. Medical system risk estimates include loss of crew life (LOCL), consideration of medical evacuation (known as return to definitive care – RTDC), and an estimate of crew time lost due to medical conditions (Task Time Lost – TTL). The presentation will also describe the medical conditions that are the greatest drivers of risk as well as the clinical capabilities and resources that have the largest effect on risk. RESULTS: All three DRMs had very low probability of LOCL from medical conditions, primarily due to short duration. RTDC was also similar across the DRMs. In contrast, TTL was higher in the early lunar sortie DRM due to earlier occurrence of EVA-related medical conditions. Taken as a whole, there was no clinically significant difference in medical risk across the three missions. Results for clinical capabilities and an example medical equipment list will be discussed but were similar across DRMs.

D Hilmers↗

Preliminary Medical Risk Estimates and Clinical Capability Needs for Late Artemis Missions

BACKGROUND Human exploration spaceflight missions to the Moon and Mars present unprecedented challenges for in- mission medical care. Compared with the ISS, the greater distance from Earth will mean increased mission durations, communication delays, limited to no resupply opportunities, and significant limitations on the evacuation of ill or injured crew. Spacecraft mass, volume, and power will be curtailed while higher demands will be placed on the crew’s knowledge, skills, and abilities. In this higher risk environment, it is important to: a) quantitatively estimate human system risk attributable to medical conditions, a process known as Probabilistic Risk Analysis, and b) use these estimates to inform medical system design. IMPACT (Informing Mission Planning via Analysis of Complex Tradespaces) is a PRA and medical trade space analysis tool developed by NASA to advance exploration mission medical system design. IMPACT v1.0 improves upon and will soon replace NASA’s existing tool, the Integrated Medical Model, with: a novel evidence base baselined to exploration environments; an expanded list of 119 medical conditions; a significant increase in the number of medical resources that can be utilized and in the flexibility of their use; and the modelling of time lost performing mission-specific tasks due to medical conditions. METHODOLOGY: This abstract will present IMPACT estimates of medical system risk and clinical capability needs for the Artemis IV mission. Artemis IV is currently scheduled for 2026 and will visit the Gateway space station in lunar orbit prior to the second lunar landing of the Artemis program. The baseline Artemis IV mission that was modeled was 28 days in duration with phases including Orion outbound, 4 days on the Gateway space station in lunar orbit, 2 crew on the surface of the Moon for approximately one week, an additional 5 days on Gateway, and then return to Earth. This baseline was compared to two alternative 34-day design reference missions (DRMs) that shifted the lunar sortie earlier or later in the mission profile. Assumptions included 2 female and 2 male crew and a notional medical system mass of 25 kg. Medical system risk estimates include loss of crew life (LOCL), consideration of medical evacuation (known as return to definitive care – RTDC), and an estimate of crew time lost due to medical conditions (Task Time Lost – TTL). The presentation will also describe the medical conditions that are the greatest drivers of risk as well as the clinical capabilities and resources that have the largest effect on risk. RESULTS: All three DRMs had very low probability of LOCL from medical conditions, primarily due to short duration. RTDC was also similar across the DRMs. In contrast, TTL was higher in the early lunar sortie DRM due to earlier occurrence of EVA-related medical conditions. Taken as a whole, there was no clinically significant difference in medical risk across the three missions. Results for clinical capabilities and an example medical equipment list will be discussed but were similar across DRMs.

D. Hilmers↗

Modeling of Mixed-Pixel Clumping Index From Remote Sensing Data and Its Evaluation

The clumping index (CI) is a canopy structure parameter that describes the dispersion or grouping of leaves. Previously, it has been estimated based on the normalized difference between hotspot and darkspot (NDHD), which is derived from multi-angle remote sensing data. However, currently it is impossible to derive CI from NDHD for a large area at a spatial resolution finer than 275 m since such fine multi-angle data are unavailable. In this study, an algorithm of the mixed-pixel clumping index (MPCI) was implemented, and an MPCI map of China's landmass at 1 km resolution was derived from the HJ-1A/1B data at 30 m resolution. The MPCI map was compared with the previous NDHD CI derived from the moderate resolution imaging spectroradiometer (MODIS). The correlation of these two datasets was greater than 0.9, and the mean bias was approximately 0.1. Indirectly, the MPCI map was applied to an effective leaf area index (LAI) product to derive true LAI. Using the MODIS LAI product as a reference, we found that the coefficient of determination was improved from 0.72 to 0.80, and the root mean squared error was reduced from 0.53 to 0.35 m 2 /m 2 after the effective LAI is corrected by this MPCI map, suggesting that this MPCI map is comparable to the NDHD CI. Although our algorithm is currently tested at 1 km resolution, potentially, it can be applied to higher spatial resolution than 275 m for mapping LAI and carbon cycle modeling before these multi-angle data at higher resolution are available.

47 OTHER INSTRUMENTATION↗

Actinium–DOTA coordination in water from hybrid ML/MM: Structure, free energies, and water-exchange pathways

Quantitative simulation of trivalent ƒ-block chelates in water remains challenging because bonded and non-bonded force-field models make different approximations for coordination structure, exchange dynamics, and ion–ligand interactions in highly charged systems. Here, we develop a hybrid machine-learning/molecular-mechanics (ML/MM) framework for Ac 3+ –DOTA in explicit solvent by training an E(3)-equivariant neural network potential (MACELES) on mechanically embedded QM/MM data for Ac aquo and Ac–DOTA species and coupling it to NAMD 2.14 with particle-mesh Ewald electrostatics. Nanosecond ML/MM trajectories remain numerically stable and preserve chelate integrity, yielding a compact DOTA inner shell with an inner-sphere water coordination number of CN Ac,O w ≈ 1.7 arising from a dynamic equilibrium between one- and two-water states (37.5% and 59.9% of frames; three waters 2.5%). A 5 ns potential of mean force shows two low-lying basins at CN Ac,O w ≈ 1 and CN Ac,O w ≈ 2. DFT end-state free energies are consistent with the ML/MM profile, and DFT minimum-energy paths provide a qualitative electronic-structure reference for the observed basin connectivity. State-resolved kinetics reveal picosecond water-exchange pathways that couple hydration changes to transient DOTA arm fluctuations, and training-set comparisons show that temperature-matched Ac–DOTA data optimize energy/force accuracy while more diverse solvated data improve charge prediction. Overall, the present hybrid ML/MM model provides a practical description of Ac 3+ –DOTA hydration thermodynamics and short-time exchange behavior in explicit water at MD-like cost.

Actinium↗

Machine learning and deep learning for mineralogy interpretation and CO 2 saturation estimation in geological carbon Storage: A case study in the Illinois Basin

Carbon capture and storage (CCS) is a promising approach to simultaneously maintaining energy security and reducing carbon dioxide (CO 2 ) emissions under the current energy portfolio that is dominated by fossil fuel energy. Pre-injection formation characterization and post-injection CO 2 monitoring are two critical tasks to guarantee storage efficiency in CCS. The CCS projects in the Illinois Basin, the first large-scale CO 2 injection into saline aquifers in the United States, employed conventional and the latest pulsed neutron logging (PNL) tools for mineralogy interpretation and CO 2 saturation estimation, which provide valuable references for future CCS projects. Because of the inherent fuzziness of petrophysical measurements and complex subsurface heterogeneity, interpreting well-logging data is time-consuming, and its accuracy can be user-biased. In recent years, data-driven methods have been widely used to capture the non-linear patterns between input features and interpretation results. This work applied and evaluated four commonly used machine learning (ML) models, including ridge regression (RR), random forest (RF), gradient boosting regression (GBR), support vector regression (SVR), and one deep learning (DL) model, the artificial neural network (ANN). We optimized the hyperparameters of the four ML models and the DL model using the simulated annealing algorithm and the grid search strategy, respectively. The input features of the mineralogy interpretation models were eleven conventional well-logging parameters, and the label data (i.e., ground truth) were the porosity and volumetric fractions of six minerals, including quartz, feldspar, dolomite, calcite, clay, and iron minerals. The results demonstrated that the GBR and RF models were superior in predicting volumetric fractions of minerals and porosity; label data with low coefficient of variation (CV) values tended to yield better performance. For CO 2 saturation estimation, the RF was the best-performing model, followed by SVR, ANN, GBR, and RR. Furthermore, we conducted feature importance ranking using the permutation importance algorithm and found that the formation sigma and well pressure were the most important features in this study. In conclusion, the study of CCS projects in the Illinois Basin bridges the gap between the limited knowledge and understanding of geological carbon storage and the increasing demand for reliable, cost-effective, and sustainable energy solutions.

58 GEOSCIENCES↗

Minkowski conformal blocks and the Regge limit for Sachdev-Ye-Kitaev-like models

We discuss scattering in a conformal field theory (CFT) via the conformal partial-wave analysis and the Regge limit. The focus of this paper is on understanding an operator product expansion (OPE) with Minkowski conformal blocks. Starting with a t-channel OPE, it leads to an expansion for an s-channel scattering amplitude in terms of t-channel exchanges. By contrasting with Euclidean conformal blocks we see a precise relationship between conformal blocks in the two limits without preforming an explicit analytic continuation. We discuss a generic feature for a CFT correlation function having singular F (M) (u,v) ~ u –δ , δ > 0, in the limit u → 0 and v → 1. Here, δ = (ℓ eff – 1)/2, with ℓ eff serving as an effective spin and it can be determined through an OPE. In particular, it is bounded from above, ℓ eff ≤ 2, for all CFTs with a gravity dual, and it can be associated with string modes interpolating the graviton in AdS. This singularity is historically referred to as the Pomeron. This bound is nearly saturated by SYK-like effective d = 1 CFT, and its stringy and thermal corrections have piqued current interests. Our analysis has been facilitated by dealing with Wightman functions. We provide a direct treatment in diagonalizing dynamical equations via harmonic analysis over physical scattering regions. As an example these methods are applied to the SYK model.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

MnEdgeNet for accurate decomposition of mixed oxidation states for Mn XAS and EELS L2,3 edges without reference and calibration

Accurate decomposition of the mixed Mn oxidation states is highly important for characterizing the electronic structures, charge transfer and redox centers for electronic, and electrocatalytic and energy storage materials that contain Mn. Electron energy loss spectroscopy (EELS) and soft X-ray absorption spectroscopy (XAS) measurements of the Mn L2,3 edges are widely used for this purpose. To date, although the measurements of the Mn L2,3 edges are straightforward given the sample is prepared properly, an accurate decomposition of the mix valence states of Mn remains non-trivial. For both EELS and XAS, 2+, 3+, and 4+ reference spectra need to be taken on the same instrument/beamline and preferably in the same experimental session because the instrumental resolution and the energy axis offset could vary from one session to another. To circumvent this hurdle, in this study, we adopted a deep learning approach and developed a calibration-free and reference-free method to decompose the oxidation state of Mn L2,3 edges for both EELS and XAS. A deep learning regression model is trained to accurately predict the composition of the mix valence state of Mn. To synthesize physics-informed and ground-truth labeled training datasets, we created a forward model that takes into account plural scattering, instrumentation broadening, noise, and energy axis offset. With that, we created a 1.2 million-spectrum database with 1-by-3 oxidation state composition ground truth vectors. The library includes a sufficient variety of data including both EELS and XAS spectra. By training on this large database, our convolutional neural network achieves 85% accuracy on the validation dataset. We tested the model and found it is robust against noise (down to PSNR of 10) and plural scattering (up to t/λ = 1). We further validated the model against spectral data that were not used in training. In particular, the model shows high accuracy and high sensitivity for the decomposition of Mn 3 O 4 , MnO, Mn 2 O 3 , and MnO 2 . The accurate decomposition of Mn 3 O 4 experimental data shows the model is quantitatively correct and can be deployed for real experimental data. Our model will not only be a valuable tool to researchers and material scientists but also can assist experienced electron microscopists and synchrotron scientists in the automated analysis of Mn L edge data.

25 ENERGY STORAGE↗

Confinement effects on the solvation structure of solvated alkaline metal cations in a single-digit 1T-MoS 2 nanochannel: A first-principles study

Confinement plays an important role in determining ion transport in porous materials, which, in turn, may influence the performance of many energy storage and desalination devices. In this work, we combined density functional theory (DFT) with an implicit solvation model and ab initio molecular dynamics (AIMD) to investigate the effects of nanoconfinement on several solvated alkaline metal cations in a single-digit 1T-MoS 2 nanochannel. Our DFT calculations with a solvation model indicated that cations with stronger hydration energy introduce a higher number of co-intercalated water molecules into the channel, consistent with early experimental observation obtained for MXene (2D transition metal carbide) channels. The predicted optimal water numbers for the cations were then used for AIMD simulations that explicitly include the effects of the solvent. When compared with the cations in bulk solution, our simulations showed that the hydration structure and coordination number (CN) of the solvated cations confined in the MoS 2 channel can be significantly altered. Further, we found that larger cations with weaker hydration energy (K + , Rb + , and Cs + ) exhibited a distinctive CN decrease under confinement, while smaller cations (Li + and Na + ) retained a similar hydration shell as in the bulk solution. More specifically, the hydration shell of large cations (K + , Rb + , and Cs + ) in MoS 2 showed similar features of the coordination angle to the bulk, which suggests the partially broken hydration shell with no geometry change under confinement. Our simulations provided insights into the change of the hydration structure of alkaline metal cations under confinement, which may have important implications on their transport in the 1T-MoS 2 channel.

36 MATERIALS SCIENCE↗

Isomer-resolved unimolecular dynamics of the hydroperoxyalkyl intermediate (•QOOH) in cyclohexane oxidation

The oxidation of cycloalkanes is important in the combustion of transportation fuels and in atmospheric secondary organic aerosol formation. A transient carbon-centered radical intermediate (•QOOH) in the oxidation of cyclohexane is identified through its infrared fingerprint and time- and energy-resolved unimolecular dissociation dynamics to hydroxyl (OH) radical and bicyclic ether products. Although the cyclohexyl ring structure leads to three nearly degenerate •QOOH isomers (β-, γ-, and δ-QOOH), their transition state (TS) barriers to OH products are predicted to differ considerably. Selective characterization of the β-QOOH isomer is achieved at excitation energies associated with the lowest TS barrier, resulting in rapid unimolecular decay to OH products that are detected. A benchmarking approach is employed for the calculation of high-accuracy stationary point energies, in particular TS barriers, for cyclohexane oxidation (C 6 H 11 O 2 ), building on higher-level reference calculations for the smaller ethane oxidation (C 2 H 5 O 2 ) system. The isomer-specific characterization of β-QOOH is validated by comparison of experimental OH product appearance rates with computed statistical microcanonical rates, including significant heavy-atom tunneling, at energies in the vicinity of the TS barrier. Master-equation modeling is utilized to extend the results to thermal unimolecular decay rate constants at temperatures and pressures relevant to cyclohexane combustion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synergistic Retrieval of Temperature and Humidity Profiles from Space-Based and Ground-Based Infrared Sounders Using an Optimal Estimation Method

The atmospheric temperature and humidity profiles of the troposphere are generally measured by radiosondes and satellites, which are essential for analyzing and predicting weather. Nevertheless, the insufficient observation frequencies and low detection accuracy of the boundary layer restricts the description of atmospheric state changes by the temperature and humidity profiles. Therefore, this work focus on retrieving the temperature and humidity profiles using observations of the FengYun-4 (FY-4) Geostationary Interferometric Infrared Sounder (GIIRS) combined with ground-based infrared spectral observations from the Atmospheric Emitted Radiance Interferometer (AERI), which are more accurate than space-based individual retrieval results and have a wider effective retrieval range than ground-based individual retrieval results. Based on the synergistic observations, which are made by matching the space-based and ground-based data with those of different spatial and temporal resolutions, a synergistic retrieval process is proposed to obtain the temperature and humidity profiles at a high frequency under clear-sky conditions based on the optimal estimation method. In this research, using the line-by-line radiative transfer model (LBLRTM) as the forward model for observing simulations, a retrieval experiment was carried out in Qingdao, China, where an AERI is situated. Taking radiosonde data as a reference for comparing the retrieval results of the temperature and humidity profiles of the troposphere, the root-mean-square error (RMSE) of the synergistic retrieval algorithm below 400 hPa is within 2 K for temperature and within 12% for relative humidity. Compared with the GIIRS individual retrieval, the RMSE of temperature and relative humidity for the synergistic method is reduced by 0.13–1.5 K and 2.7–4.4% at 500 hPa, and 0.13–2.1 K and 2.5–7.2% at 900 hPa. Moreover, the forecast index (FI) calculated from the retrieval results shows reasonable consistency with the FIs calculated from the ERA5 reanalysis and from radiosonde data. The synergistic retrieval results have higher temporal resolution than space-based retrieval results and can reflect the changes in the atmospheric state more accurately. Overall, the results demonstrated the promising potential of the synergistic retrieval of temperature and humidity profiles at high accuracy and high temporal resolution under clear-sky conditions from FY-4/GIIRS and AERI.

54 ENVIRONMENTAL SCIENCES↗