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At least 127 records · Page 7

Assessing Uncertainties and Approximations in Solar Heating of the Climate System

In calculating solar radiation, climate models make many simplifications, in part to reduce computational cost and enable climate modeling, and in part from lack of understanding of critical atmospheric information. Whether known errors or unknown errors, the community's concern is how these could impact the modeled climate. The simplifications are well known and most have published studies evaluating them, but with individual studies it is difficult to compare. Here, we collect a wide range of such simplifications in either radiative transfer modeling or atmospheric conditions and assess potential errors within a consistent framework on climate-relevant scales. We build benchmarking capability around a solar heating code (Solar-J) that doubles as a photolysis code for chemistry and can be readily adapted to consider other errors and uncertainties. The broad classes here include: use of broad wavelength bands to integrate over spectral features; scattering approximations that alter phase function and optical depths for clouds and gases; uncertainty in ice-cloud optics; treatment of fractional cloud cover including overlap; and variability of ocean surface albedo. We geographically map the errors in W m -2 using a full climate re-creation for January 2015 from a weather forecasting model. For many approximations assessed here, mean errors are ~2 W m -2 with greater latitudinal biases and are likely to affect a model’s ability to match the current climate state. Combining this work with previous studies, we make priority recommendations for fixing these simplifications based on both the magnitude of error and the ease or computational cost of the fix.

58 GEOSCIENCES↗

Calibration of V-Notch and Compound Weirs for Subsurface Drainage Water Level Control Structures

Highlights Accurate discharge estimation is important when evaluating edge-of-field conservation practices. V-notch weir equations were developed for three sizes of subsurface drainage water level control structures. Compound weir equations were developed for subsurface drainage water level control structures. The compound weir equation accurately estimates discharge for flows within and overtopping the V-notch. Abstract.Numerous edge-of-field conservation practices use subsurface drainage water level control structures to monitor water levels and estimate discharge. In a control structure, procedures for calculating discharge when flow depth (head) exceeds the V-notch depth and overflows in the rectangular portion of the compound weir (CW) are ambiguous. In this study, we developed calibration equations for V-notch weirs in Agri Drain inline water level control structures of different sizes for flows within the V-notch and overtopping flow events. The discharge equation for overtopping events (Q CW , L s -1 ) was determined as: Q CW = a 1 (h b1 -h 1 b1 )+a 2 (W e -W v )h 1 b2 , where h and h 1 are heads above vertex/bottom and top of V-notch (cm), respectively, W is the effective crest width of rectangular weir (cm), W v is the top width of V-notch (cm), a 1 and b 1 are parameters for V-notch weir obtained by calibration, and a 2 and b 2 are calibration parameters for rectangular weir obtained from literature. Results were compared with a weir equation available in the literature (Q V+R ), which combines a V-notch equation with a head equal to V-depth and a rectangular weir equation for flow above V-depth. Discharge at overflow was estimated with high accuracy with Q CW, whereas Q V+R underestimated discharge (e.g., PBIAS of 0.67% vs. 17.82% for a 15.2 cm structure). An example using Q V+R resulted in a 14% lower annual estimation of nitrate-N load diverted to a saturated buffer than Q CW due to underestimation of drainage discharge during overflow events. Results suggest that the developed equation (Q CW ) accurately estimates discharge and will thus improve the estimated N load compared to Q V+R . Keywords: Compound weir, Flow monitoring, Subsurface drainage, V-notch weir, Water level control structure, Weir calibration.

Agriculture↗

Multiwell Fiber Optic Sensing Reveals Effects of CO2 Flow on Triggered Seismicity

Induced seismicity is one of the main risks for gigaton-scale geological storage of carbon dioxide (⁠CO 2 ⁠). Thus, passive seismic monitoring is often recommended as a necessary component of the monitoring systems for CO 2 storage projects, with a particular forcus on risk mitigation. We present the first field study, CO2CRC Otway Project Stage 3 (Victoria, Australia), where distributed acoustic sensing (DAS) enabled high-precision tracking of the induced seismicity triggered by a small CO 2 injection and also informed the reservoir models. In 610 days of passive seismic monitoring of the Stage 3 injection, we detected 17 microseismic events (maximum moment magnitude Mw 0.1) using five deep boreholes equipped with enhanced-sensitivity optical fiber. The DAS array has sensitivity sufficient for detection and location of induced events with M w ~ ₋2 in a monitoring borehole located up to 1500 m away. Thanks to the dense spatial sampling by the DAS, we were able to estimate the focal mechanisms for events with M w > ₋1.5; although the monitoring boreholes provided very limited angular coverage. The main cluster of the events has the same location and source mechanism as the one triggered by the previous CO 2 injection at the Otway Project site, Stage 2C. Surprizingly, the Stage 2C and Stage 3 events closely followed the actual movement of the CO 2 saturation plume front (not the pressure front), as observed using controlled-source reflection seismic images. The nature of the plume-fault interaction remains unclear, but some alteration of the fault gouge by CO 2 might be responsible for the faults’ reactivation by the pressure perturbation. Importantly, the seismogenic fault could not be identified in the seismic images and was only revealed by DAS observations, which also demonstrated the signature of fluid–rock interaction, that may control the CO 2 flow.

58 GEOSCIENCES↗

Multiscale Land-Atmosphere Interaction in Tropical Ecosystems

A leading source of uncertainty in the magnitude of future climate change arises from feedback between the physical climate system and the carbon cycle. Output from 15 Earth System Models (ESMs) in the Coupled Model Intercomparison Project (CMIP5) shows that when forced by identical emissions, predicted atmospheric CO 2 concentrations in 2100 ranged from 780 ppm to 1120 ppm due to variations in carbon cycle feedback among the models. The resulting difference in radiative forcing of climate is almost 2 W m -2 , comparable to the total uncertainty in the physical climate system for the representative concentration pathway (RCP) 8.5 scenario in 2100. Scaling future carbon sources and sinks to match contemporary atmospheric CO 2 reduced this uncertainty by a factor of five, suggesting that contemporary observations might dramatically constrain future predictions, but their scaling had no mechanistic basis, so it provides little insight on carbon cycle processes.

54 ENVIRONMENTAL SCIENCES↗

Magnetostrictive Brake

A magnetostrictive brake has been designed as a more energy-efficient alternative to a magnetic fail-safe brake in a robot. (In the specific application, failsafe signifies that the brake is normally engaged; that is, power must be supplied to allow free rotation.) The magnetic failsafe brake must be supplied with about 8 W of electric power to initiate and maintain disengagement. In contrast, the magnetostrictive brake, which would have about the same dimensions and the same torque rating as those of the magnetic fail-safe brake, would demand only about 2 W of power for disengagement. The brake (see figure) would include a stationary base plate and a hub mounted on the base plate. Two solenoid assemblies would be mounted in diametrically opposed recesses in the hub. The cores of the solenoids would be made of the magnetostrictive alloy Terfenol-D or equivalent. The rotating part of the brake would be a ring-and spring- disk subassembly. By means of leaf springs not shown in the figure, this subassembly would be coupled with the shaft that the brake is meant to restrain. With no power supplied to the solenoids, a permanent magnet would pull axially on a stepped disk and on a shelf in the hub, causing the ring to be squeezed axially between the stepped disk and the hub. The friction associated with this axial squeeze would effect the braking action. Supplying electric power to the solenoids would cause the magnetostrictive cylinders to push radially inward against a set of wedges that would be in axial contact with the stepped disk. The wedges would convert the radial magnetostrictive strain to a multiplied axial displacement of the stepped disk. This axial displacement would be just large enough to lift the stepped disk, against the permanent magnetic force, out of contact with the ring. The ring would then be free to turn because it would no longer be squeezed axially between the stepped disk and the hub.

Diftler, Myron A.↗

Charon/Pluto Mass Ratio Obtained with HST CCD Observations in 1991 and 1993

We have analyzed Hubble Space Telescope wide field camera observations of Pluto, Charon, and a reference star, acquired in 1991 and 1993, to observe Pluto's barycentric motion and determine the Charon/Pluto mass ratio, q = 0.1237 +/-0.0081, with 6.5% accuracy. Solution values for Charon orbital elements include the semimajor axis, a = 19662 +/-81 km; inclination, i = 96.57 +/-0.24 deg; eccentricity, e = 0.0072 +/-0.0067; longitude of periapsis, w = 2 +/-35 deg; and mean longitude, l = 123.58 +/-0.43 deg. These elements are referred to the J2000 Earth equator and equinox at epoch JED 2446600.5.

Charon Pluto↗

Effective Storage of Electrons in Water by the Formation of Highly Reduced Polyoxometalate Clusters

Aqueous solutions of polyoxometalates (POMs) have been shown to have potential as high-capacity energy storage materials due to their potential for multi-electron redox processes, yet the mechanism of reduction and practical limits are currently unknown. Herein, we explore the mechanism of multi-electron redox processes that allow the highly reduced POM clusters of the form {MO 3 } y to absorb y electrons in aqueous solution, focusing mechanistically on the Wells-Dawson structure X 6 [P 2 W 18 O 62 ], which comprises 18 metal centers and can uptake up to 18 electrons reversibly (y = 18) per cluster in aqueous solution when the countercations are lithium. This unconventional redox activity is rationalized by density functional theory, molecular dynamics simulations, UV-vis, electron paramagnetic resonance spectroscopy, and small-angle X-ray scattering spectra. These data point to a new phenomenon showing that cluster protonation and aggregation allow the formation of highly electron-rich meta-stable systems in aqueous solution, which produce H 2 when the solution is diluted. Finally, we show that this understanding is transferrable to other salts of [P 5 W 30 O 110 ] 15- and [P 8 W 48 O 184 ] 40- anions, which can be charged to 23 and 27 electrons per cluster, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Feasibility for Orbital Life Extension of a CubeSat in the Lower Thermosphere

Orbital flight of CubeSats at altitudes between 150 and 250 km has the potential to enable a new class of scientific, commercial, and defense-related missions. A study is presented to demonstrate the feasibility of extending the orbital lifetime of a CubeSat in a 210 km orbit. Propulsion consists of an electrospray thruster operating at a 2 W, 0.175 mN thrust, and an specific impulse (Isp) of 500 s. The mission consists of two phases. In phase 1, the CubeSat is deployed from a 414 km orbit and uses the thruster to deorbit to the target altitude of 210 km. In phase 2, the propulsion system is used to extend the mission lifetime until propellant is fully expended. A control algorithm based on maintaining a target orbital energy is presented that uses an extended Kalman filter to generate estimates of the orbital dynamic state, which are periodically updated by Global Positioning System measurements. For phase 1, the spacecraft requires 25.21 days to descend from 414 to 210 km, corresponding to a delta V = 96.25 m/s and a propellant consumption of 77.8 g. Phase 2 lasts 57.83 days, corresponding to a delta V = 119.15 m/s, during which the remaining 94.2 g of propellant are consumed.

Blandino, John J.↗

Large change of interlayer vibrational coupling with stacking in Mo 1-x W x Te 2

Stacking variations in quasi-two-dimensional materials can have an important influence on material properties, such as changing the topology of the band structure. Unfortunately, the weakness of van der Waals (vdW) interactions makes it difficult to compute the stacking dependence of properties, and even in a material as simple as graphite the stacking energetics remain unclear. Mo 1 - x W x Te 2 is a material in which three differently stacked phases are conveniently accessible by temperature changes: 1 T ' , T d * , and the reported Weyl semimetal phase T d . Additionally, the transitions proceed via layer sliding, and the corresponding interlayer shear mode (ISM) is relevant not just for the stacking energetics but also for understanding the relationship between Weyl physics and structural changes. However, the interlayer interactions of Mo 1 - x W x Te 2 are not well understood, with wide variation in computed properties. We report inelastic neutron scattering of the ISM in a Mo 0.91 W 0.09 Te 2 crystal. The ISM energies are generally consistent with the linear chain model, as expected given the weak interlayer interaction, though there are some discrepancies from predicted intensities. However, the interlayer force constants K x in the T d * and 1 T ' phases are substantially weaker than that of T d at 75(3) and 83(3)%, respectively. Considering that the relative positioning of atoms in neighboring layers is approximately the same regardless of overall stacking, our results suggest that longer-range influences, such as stacking-induced electronic band-structure changes, may be responsible for the substantial change in the interlayer vibrational coupling and thus the C 55 elastic constant. These findings should elucidate the stacking energetics of Mo 1 - x W x Te 2 and other vdW layered materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ionothermally Synthesized Nanoporous Ti 0.95 W 0.05 Nb 2 O 7 : a Novel Anode Material for High-Performance Lithium-Ion Batteries

Although TiNb 2 O 7 is regarded as a fast-rechargeable lithium-ion battery (LIB) anode material, the intrinsic poor electrochemical kinetics of TiNb 2 O 7 still dramatically impedes its development. Herein, an ionothermal synthesis-assisted doping strategy is proposed for the preparation of a new W 6+ -doped TiNb 2 O 7 material (Ti 0.95 W 0.05 Nb 2 O 7 ) with nanoporous structure (denoted as NPTWNO). The improved Li + diffusion coefficient of NPTWNO suggests that the ionic-liquid-templated nanoporous architecture improves the Li+ diffusion kinetics. The density functional theory computational study reveals that the doped W 6+ successfully boosts the electronic conductivity due to the narrowed conduction-valance bandgap resulted from charge redistribution, which is reflected by the electrochemical impedance spectroscopy data. With the simultaneously enhanced Li+ diffusivity and electronic conductivity, NPTWNO achieves fast-rechargeability in LIBs. So this work indicates the potential of ionothermal synthesis-assisted doping strategy on energy storage materials and offers NPTWNO material with promising electrochemical performance.

25 ENERGY STORAGE↗

Small-Molecule Models of Hydrogen-Evolving MX 2 (M = Mo, W; X = S, Se) Bulk Solids: Composition–Activity Relationships

Triangular metal chalcogenide clusters of the form [M 3 Q 7 L 3 ]An (M = Mo or W; Q = S or Se; L = i Bu 2 NCS 2 – , (CF 3 CH 2 ) 2 NCS 2 – , i Bu 2 NCSe 2 – , or i Bu 2 PS 2 – ; An = Cl – or I – ) have been investigated as molecular analogues of layered metal dichalcogenide (MX 2 ) H 2 -evolution catalysts. These clusters have been evaluated for their relative H 2 -evolving ability under a common photolysis protocol implementing [Ru(bpy) 3 ] 2+ as chromophore and Et 3 N as sacrificial electron donor. With M constant as Mo and with constant supporting ligand, clusters with an all-sulfide core enable greater H 2 -TON than clusters with an all-selenide core. A more active catalyst is produced by [Mo 3 S 7 (S 2 CN i Bu 2 ) 3 ] + I – than its W 3 analogue with the same core sulfide composition and supporting dithiocarbamate ligands. Dichalcogenocarbamate ligands provide more active catalysts than dialkyldithiophosphate ligated clusters, and within the dichalcogenocarbamate set, greater H 2 -turnovers correlate with more-electron-donating ligands (i.e., i Bu 2 NCS 2 – > (CF 3 CH 2 ) 2 NCS 2 – > i Bu 2 NCSe 2 – ). Cluster cations with Cl – as counteranion are very similar in activity H 2 -evolving levels to identical clusters with I – , ruling out any significant interfering effect by I – upon the electron transfer relay between Et 3 N and catalyst. In the aggregate, observations are consistent with a mechanism for H 2 evolution that involves reductive extrusion of H 2 from a metal hydride intermediate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of the interaction between SiC, pre-oxidized FeCrAlMo with aluminized and pre-oxidized Fe-8Cr-2W in flowing PbLi

We report dissimilar materials interactions are a major concern when liquid metals are used as a working fluid. To simulate a dual-coolant PbLi blanket, chemical vapor deposited (CVD) SiC, pre-oxidized FeCrAlMo (APMT) and pre-oxidized aluminized coating on Fe-8Cr-2 W (F82H) specimens were exposed to flowing commercial Pb-17at.%Li with a peak temperature of 650 °C in a pre-oxidized APMT thermal convection loop (TCL) for 1000 h. Similar to prior results in static PbLi, the coated F82H showed small mass changes and limited degradation of room-temperature tensile properties. After exposure, the α-Al 2 O 3 on the surface coated F82H reacted with the PbLi to form LiAlO 2 . However, no significant Al coating loss or interdiffusion was observed. Mass transfer was observed between the APMT, TCL and the SiC specimens. Fe, Cr and Ni were dissolved into the molten flowing PbLi and transported through the TCL to react with the SiC specimens. Compared to a prior experiment with a majority of bare FeCrAl specimens that were exposed in a TCL with a peak temperature of 700 °C for 1000 h, the SiC reaction was reduced to only a few microns of carbides and silicides. Oxygen dissolved in the molten PbLi sustained the formation of an Al 2 O 3 scale on the surface of the coating and induced the formation of a thin surface SiO 2 layer on the surface of the SiC.

36 MATERIALS SCIENCE↗

Low thermal conductivity in Bi 8 CsO 8 SeX 7 (X = Cl, Br) by combining different structural motifs

Understanding the structure–property relationships of materials in order to supress thermal conductivity is crucial for developing efficient thermoelectric generators and thermal barrier coatings. Low thermal conductivity materials can often contain a single dominant phonon scattering mechanism. Here, we highlight how combining different structural features into one material can aid in the design and identification of new materials with low thermal conductivities. We synthesise two new mixed-anion materials, Bi 8 CsO 8 SeX 7 (X = Cl and Br), with low thermal conductivities of 0.27(2) and 0.22(2) W m -1 K -1 respectively, measured along their c-axes at room temperature. The Bi 8 CsO 8 SeX 7 materials possess a combination of bond strength hierarchies, Cs + vacancies, and low frequency Cs + rattling. These different features significantly inhibit phonon transport along different crystallographic directions. Due to sharp bond strength contrast between the van der Waals gaps and [Bi 2 O 2 ] 2+ layers, the Bi 8 CsO 8 SeX 7 materials exhibit thermal conductivities <50% of the theoretical minimum when measured along the stacking direction. Conversely, the thermal conductivity associated with the ab-plane is reduced by Cs + rattling when compared to the structurally and compositionally related BiOCl.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strategies for the Photoreduction of Tc-99 Pertechnetate to Low-Valent Tc by Keggin Polyoxometalates

Technetium-99 (half-life of 2.1 × 10 5 yrs, β max = 0.29 MeV) is a hazardous radiological contaminant, which, in its predominant form of pertechnetate (TcO 4 – ), is highly mobile in the environment. Most strategies for the removal of pertechnetate from the environment involve uptake and/or absorption of pertechnetate using resins, clays, cationic metal-organic frameworks and even thorium borate ceramic like materials. Alternative approaches have involved the reduction and subsequent sequestration of lower valent technetium species using iron, sulfides, or iron sulfides. Here, our lab has explored this strategy using the lacunary alpha-2 Wells–Dawson polyoxometalate (α 2 -[P 2 W 17 O 61 ] 10– ) to both reduce and sequester lower valent technetium, and we have reported on the ligand features that stabilize the reduced species. In this work we investigate the potential of “plenary” Keggin POMs (XW 12 O 40 n – ) (X = P, Si, Al, n = 3, 4, 5, respectively) to both reduce TcO 4 – and stabilize the reduced Tc species. Specifically, we report on the mechanism by which the reduction of technetium occurs and find that PW 12 , SiW 12 , and AlW 12 promote the reduction of TcO 4 – to lower valent states. X-ray absorption spectroscopy was used to confirm a combination of Tc IV {in the form of TcO 2 · 2H 2 O and Tc 2 (µ-O) 2 4+ } and Tc V , which is subsequently complexed into a POM defect as a Tc V =O species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Local structure elucidation of tungsten-substituted vanadium dioxide (V$$_{1-x}$$W$$_x$$O$$_2$$)

Abstract Initially, vanadium dioxide seems to be an ideal first-order phase transition case study due to its deceptively simple structure and composition, but upon closer inspection there are nuances to the driving mechanism of the metal-insulator transition (MIT) that are still unexplained. In this study, a local structure analysis across a bulk powder tungsten-substitution series is utilized to tease out the nuances of this first-order phase transition. A comparison of the average structure to the local structure using synchrotron x-ray diffraction and total scattering pair-distribution function methods, respectively, is discussed as well as comparison to bright field transmission electron microscopy imaging through a similar temperature-series as the local structure characterization. Extended x-ray absorption fine structure fitting of thin film data across the substitution-series is also presented and compared to bulk. Machine learning technique, non-negative matrix factorization, is applied to analyze the total scattering data. The bulk MIT is probed through magnetic susceptibility as well as differential scanning calorimetry. The findings indicate the local transition temperature ( $$T_c$$ T c ) is less than the average $$T_c$$ T c supporting the Peierls-Mott MIT mechanism, and demonstrate that in bulk powder and thin-films, increasing tungsten-substitution instigates local V-oxidation through the phase pathway VO $$_2\, \rightarrow$$ 2 → V $$_6$$ 6 O $$_{13} \, \rightarrow$$ 13 → V $$_2$$ 2 O $$_5$$ 5 .

Wilson, Catrina E. (ORCID:0000000173397318)↗

Memory and rejuvenation in glassy systems

Here, the memory effect in a single crystal spin glass (Cu 0.92 Mn 0.08 ) has been measured using 1 Hz ac susceptibility measurements over a reduced temperature range of 0.4 - 0.7 T g and a model of the memory effect has been developed. A double-waiting-time protocol is carried out where the spin glass is first allowed to age at a temperature below T g , T w$_{1}$ , followed by a second aging 4 K lower, T w$_{2}$ . The 4 K separation is sufficient to ensure rejuvenation has occurred. The model is based on calculating overlaps between the growth of the correlation lengths at the two temperatures. It accounts for the absolute magnitude of the memory effect as a function of both waiting times and temperatures. The data can be explained by the memory loss being a function of the relative change in the correlated volume at the first waiting temperature due to growth in the correlations at the second waiting temperature.

36 MATERIALS SCIENCE↗

Combustion of 10–100 μm aluminum droplets in detonation products gases

Here we describe a two-phase model of combustion effects in aluminized high explosive (HE) charges. It is based on: (i) a Gas Dynamic Model of the expansion of the detonation product gases and their turbulent combustion with air; and (ii) a Heterogeneous Continuum Model of aluminum (Al) droplets and their combustion with the detonation product gases. Initial conditions are based on an analytical similarity solution for a cylindrical Chapman-Jouguet (CJ) detonation propagating at the CJ detonation velocity. The CJ jump conditions are computed at the thermodynamic equilibrium state by the Cheetah code, assuming the Al droplets are inert. We assume that the Al is 10 % of the charge mass and occurs as droplets at the CJ state. Different initial droplet diameters, ranging from 10 to 100 microns, are studied. A hydrodynamic combustion model based on large Damköhler numbers is employed in this study, -3σ(1 + 0.276 $\sqrt{Re}$)/($Kd^2_w$). It has a square-root dependence on the Reynolds number (Re) and inversed-squared dependence on the droplet diameter (d w ). The burnout time (t B ) of the Al droplets has a three-halves dependence on the droplet diameter, t B ~ ($d^0_w$) 3/2 . After burnout, the detonation products act as detonation products of the HE charge with active Al. They turbulently mix with air and form a combustion layer on the outer edge of the fireball. Details of the two-phase model, initial conditions and evolution of the flow field will be described.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗