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DOE OSTI2021

Ideal internal kink stability in presence of plasma flow and neoclassical toroidal viscosity due to energetic particles

Abstract The influence of energetic particles (EPs) on the ideal internal kink mode, in rotating tokamak plasmas, is numerically investigated by simultaneously solving MHD-kinetic hybrid equations together with a toroidal momentum balance equation utilizing the MARS-Q code (Liu et al 2013 Phys. Plasmas 20 042503). The neoclassical toroidal viscous (NTV) torque, induced by precessional drift resonances of trapped energetic particles, acts as the momentum sink term to damp the plasma flow. Quasi-linear initial value simulations show local reduction of the flow amplitude and enhancement of the flow shear near the q = 1 rational surface ( q is the safety factor) due to EP induced NTV. Both effects in turn destabilize the internal kink mode. These numerical findings are robust against the initial linear stability of internal kink, the initial plasma flow profile, as well as the equilibrium distribution model for EPs.

Physics↗

NASA NTRS2016

Solar Array at Very High Temperatures: Ground Tests

Solar array design for any spacecraft is determined by the orbit parameters. For example, operational voltage for spacecraft in Low Earth Orbit (LEO) is limited by significant differential charging due to interactions with low temperature plasma. In order to avoid arcing in LEO, solar array is designed to generate electrical power at comparatively low voltages (below 100 V) or to operate at higher voltages with encapsulated of all suspected discharge locations. In Geosynchronous Orbit (GEO) differential charging is caused by energetic electrons that produce differential potential between coverglass and conductive spacecraft body in a kilovolt range. In such a case, weakly conductive layer over coverglass (ITO) is one of possible measures to eliminate dangerous discharges on array surface. Temperature variations for solar arrays in both orbits are measured and documented within the range of -150 C +110 C. This wide interval of operational temperatures is regularly reproduced in ground tests with radiative heating and cooling inside shroud with flowing liquid nitrogen. The requirements to solar array design and tests turn out to be more complicated when planned trajectory crosses these two orbits and goes closer to Sun. Conductive layer over coverglass causes sharp increase in parasitic current collected from LEO plasma, high temperature may cause cracks in encapsulating material (RTV), radiative heating of coupon in vacuum chamber becomes practically impossible above 150 C, conductivities of glass and adhesive go up with temperature that decrease array efficiency, and mechanical stresses grow up to critical magnitudes. A few test arrangements and respective results are presented in current paper. Coupons were tested against arcing in simulated LEO and GEO environments under elevated temperatures up to 200 C. The dependence of leakage current on temperature was measured, and electrostatic cleanness was verified for coupons with antireflection (AR) coating over ITO layer.

differential charging↗

NASA NTRS2016

Contributions of Solar Wind and Micrometeoroids to Molecular Hydrogen in the Lunar Exosphere

We investigate the density and spatial distribution of the H2 exosphere of the Moon assuming various source mechanisms. Owing to its low mass, escape is non-negligible for H2. For high-energy source mechanisms, a high percentage of the released molecules escape lunar gravity. Thus, the H2 spatial distribution for high-energy release processes reflects the spatial distribution of the source. For low energy release mechanisms, the escape rate decreases and the H2 redistributes itself predominantly to reflect a thermally accommodated exosphere. However, a small dependence on the spatial distribution of the source is superimposed on the thermally accommodated distribution in model simulations, where density is locally enhanced near regions of higher source rate. For an exosphere accommodated to the local surface temperature, a source rate of 2.2 g s-1 is required to produce a steady state density at high latitude of 1200 cm-3. Greater source rates are required to produce the same density for more energetic release mechanisms. Physical sputtering by solar wind and direct delivery of H2 through micrometeoroid bombardment can be ruled out as mechanisms for producing and liberating H2 into the lunar exosphere. Chemical sputtering by the solar wind is the most plausible as a source mechanism and would require 10-50 of the solar wind H+ inventory to be converted to H2 to account for the observations.

Impact↗

NASA NTRS2019

Satellite Salinity Observing System: Recent Discoveries and the Way Forward

Advances in L-band microwave satellite radiometry in the past decade, pioneered by ESA's SMOS and NASA's Aquarius and SMAP missions, have demonstrated an unprecedented capability to observe global sea surface salinity (SSS) from space. Measurements from these missions are the only means to probe the very-near surface salinity (top cm), providing a unique monitoring capability for the interfacial exchanges of water between the atmosphere and the upper-ocean, and delivering a wealth of information on various salinity processes in the ocean, linkages with the climate and water cycle, including land-sea connections, and providing constraints for ocean prediction models. The satellite SSS data are complimentary to the existing in situ systems such as Argo that provide accurate depiction of large-scale salinity variability in the open ocean but under-sample mesoscale variability, coastal oceans and marginal seas, and energetic regions such as boundary currents and fronts. In particular, salinity remote sensing has proven valuable to systematically monitor the open oceans as well as coastal regions up to approximately 40 km from the coasts. This is critical to addressing societally relevant topics, such as land-sea linkages, coastal-open ocean exchanges, research in the carbon cycle, near-surface mixing, and air-sea exchange of gas and mass. In this paper, we provide a community perspective on the major achievements of satellite SSS for the aforementioned topics, the unique capability of satellite salinity observing system and its complementarity with other platforms, uncertainty characteristics of satellite SSS, and measurement versus sampling errors in relation to in situ salinity measurements. We also discuss the need for technological innovations to improve the accuracy, resolution, and coverage of satellite SSS, and the way forward to both continue and enhance salinity remote sensing as part of the integrated Earth Observing System in order to address societal needs.

Vinogradova, Nadya↗

DOE OSTI2025

Unraveling Exciton Trap Dynamics and Nonradiative Loss Pathways in Quantum Dots via Atomistic Simulations

Surface defects in colloidal quantum dots are a major source of nonradiative losses, yet the microscopic mechanisms underlying exciton trapping and recombination remain elusive. Here, we develop a model Hamiltonian based on atomistic electronic calculations to investigate exciton dynamics in CdSe/CdS core/shell QDs containing a single hole trap introduced by an unpassivated sulfur atom. By systematically varying the defect depth and reorganization energy, we uncover how defect-induced excitonic states mediate energy relaxation pathways. Our simulations reveal that a single localized defect can induce a rich spectrum of excitonic states, leading to multiple dynamical regimes, from slow, energetically off-resonant trapping to fast, cascaded relaxation through in-gap defect states. Crucially, we quantify how defect-induced polaron shifts and exciton-phonon couplings govern the balance between efficient radiative emission and rapid nonradiative decay. These insights clarify the microscopic origin of defect-assisted loss channels and suggest pathways for tailoring QD optoelectronic properties via surface and defect engineering.

Defects↗

NASA NTRS1997

Laboratory Plasma Source as an MHD Model for Astrophysical Jets

The significance of the work described herein lies in the demonstration of Magnetized Coaxial Plasma Gun (MCG) devices like CPS-1 to produce energetic laboratory magneto-flows with embedded magnetic fields that can be used as a simulation tool to study flow interaction dynamic of jet flows, to demonstrate the magnetic acceleration and collimation of flows with primarily toroidal fields, and study cross field transport in turbulent accreting flows. Since plasma produced in MCG devices have magnetic topology and MHD flow regime similarity to stellar and extragalactic jets, we expect that careful investigation of these flows in the laboratory will reveal fundamental physical mechanisms influencing astrophysical flows. Discussion in the next section (sec.2) focuses on recent results describing collimation, leading flow surface interaction layers, and turbulent accretion. The primary objectives for a new three year effort would involve the development and deployment of novel electrostatic, magnetic, and visible plasma diagnostic techniques to measure plasma and flow parameters of the CPS-1 device in the flow chamber downstream of the plasma source to study, (1) mass ejection, morphology, and collimation and stability of energetic outflows, (2) the effects of external magnetization on collimation and stability, (3) the interaction of such flows with background neutral gas, the generation of visible emission in such interaction, and effect of neutral clouds on jet flow dynamics, and (4) the cross magnetic field transport of turbulent accreting flows. The applicability of existing laboratory plasma facilities to the study of stellar and extragalactic plasma should be exploited to elucidate underlying physical mechanisms that cannot be ascertained though astrophysical observation, and provide baseline to a wide variety of proposed models, MHD and otherwise. The work proposed herin represents a continued effort on a novel approach in relating laboratory experiments to astrophysical jet observation. There exists overwhelming similarity among these flows that has already produced some fascinating results and is expected to continue a high pay off in future flow similarity studies.

Mayo, Robert M.↗

DOE OSTI2021

Non-adiabatic quantum interference in the ultracold Li + LiNa → Li 2 + Na reaction

Electronically non-adiabatic effects play an important role in many chemical reactions. However, how these effects manifest in cold and ultracold chemistry remains largely unexplored. Here for the first time we present from first principles the non-adiabatic quantum dynamics of the reactive scattering between ultracold alkali-metal LiNa molecules and Li atoms. We show that non-adiabatic dynamics induces quantum interference effects that dramatically alter the ultracold rotationally resolved reaction rate coefficients. The interference effect arises from the conical intersection between the ground and an excited electronic state that is energetically accessible even for ultracold collisions. These unique interference effects might be exploited for quantum control applications such as a quantum molecular switch. The non-adiabatic dynamics are based on full-dimensional ab initio potential energy surfaces for the two electronic states that includes the non-adiabatic couplings and an accurate treatment of the long-range interactions. A statistical analysis of rotational populations of the Li2 product reveals a Poisson distribution implying the underlying classical dynamics are chaotic. The Poisson distribution is robust and amenable to experimental verification and appears to be a universal property of ultracold reactions involving alkali metal dimers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1993

The relationship between mixed Rossby-gravity waves and convection in a general circulation model

We investigate the relationship between mixed Rossby-gravity waves (MRGWs) and convection in a general circulation model. The experiments described are performed in a general circulation model with the lower boundary set to that of an ocean surface everywhere. Several experiments are run varying the convective parameterization scheme (using either a modified Kuo scheme or a moist convective adjustment scheme) and varying the tropical sea surface temperatures (specified to be zonally symmetric in all cases), thereby changing the location of the modeled intertropical convergence zones (ITCZs). The appearance of a robust MRGW occurs when the sea surface temperature is such that two ITCZs straddle the equator. The particular sea surface temperature distribution used and the parameterization scheme for convection also affect the structure and strength of the modeled MRGW. The vertical structure of MRGWs is analyzed in the experiment in which this wave mode is the most energetic. We show that MRGWs of several different zonal length scales exist in the troposphere in association with convection; however, it is only the longer length scales which can be discerned in the upper troposphere and lower stratosphere.

Hess, Peter G.↗

NASA NTRS1995

Study of the space environmental effects on spacecraft engineering materials

The space environment in which the Space Station Freedom and other space platforms will orbit is truly a hostile environment. For example, the current estimates of the integral fluence for electrons above 1 Mev at 2000 nautical miles is above 2 x 10(exp 10) electrons/sq cm/day. and the proton integral fluence is above 1 x 109 protons/sq cm/day. At the 200 - 400 nautical miles, which is more representative of the altitude which will provide the environment for the Space Station, each of these fluences will be proportionately less; however, the data indicates that the radiation environment will obviously have an effect on structural materials exposed to the environment for long durations. The effects of this combined environment is the issue which needs to be understood for the long term exposure of structures in space. In order to better understand the effect of these hostile phenomena on spacecraft, several types of studies are worth performing in order to simulate at some level the effect of the environment. For example the effect of protons and electrons impacting structural materials are easily simulated through experiments using the Van de Graff and Pelletron accelerators currently housed in the Environmental Effects Facility at MSFC. Proton fluxes with energies of 700 Kev-2.5 Mev can be generated and used to impinge on sample targets to determine the effects of the particles. Also the Environmental Effects Facility has the capability to generate electron beams with energies from 700 Kev to 2.5 Mev. These facilities will be used in this research to simulate space environmental effects from energetic particles. Ultraviolet radiation, particularly in the ultraviolet (less than 400 nm wavelength) is less well characterized at this time. The Environmental Effects Facility has a vacuum system dedicated to studying the effects of ultraviolet radiation on specific surface materials. This particular system was assembled in a previous study (NAS8-38609) in order to perform a variety of experiments on materials proposed for the Space Station. That system has continued to function as planned and has been used in carrying out portions of the proposed study.

Obrien, Susan K.↗

NASA NTRS2023

The 18–19 March 2022 Series of 3He-Rich Events Observed By Solar Orbiter at 0.36 Au Compared With EUV, X-Ray, and Radio Observations

Context. During the first close perihelion pass of Solar Orbiter, a series of impulsive 3He-rich solar particle events was observed on 18–19 March 2022 from a distance of 0.36 au. In addition to the energetic particle, radio, and X-ray data from Solar Orbiter, the events were observed in radio and/or extreme ultraviolet by STEREO-A, SDO, Wind, and Parker Solar Probe. Aims. Observations of the event series along with remote sensing of flaring and radio emission with only small timing delays due to the close distance allow the association with energetic particles to be determined with much higher accuracy than previously possible from 1 au. Methods. By comparing the onsets of type-III bursts with the arrival of electrons of tens of keV at Solar Orbiter only a few minutes later, it can be seen that, overall, each of the more intense type-III bursts was associated with an electron and ion injection. Extreme ultraviolet data show that the times of the type-III bursts coincide with emission from a small (approximately Earth-sized) loop to the west of a nearby active region. Results. The energetic particle spectra and abundances show typical properties of impulsive 3He-rich flares and, when combined with the remote sensing observations, establish that the particle-accelerating mechanism in this series of events operates near the solar surface in association with magnetic loops, and in the absence of other phenomena such as jets and small coronal mass ejections.

acceleration of particles↗

NASA NTRS2015

Electrostatic Discharge Testing of Carbon Composite Solar Array Panels for Use in the Jovian Environment

NASA is currently considering a mission to investigate the moons of Jupiter. When designing a spacecraft for this type of mission, there are a number of engineering challenges, especially if the mission chooses to utilize solar arrays to provide the spacecraft power. In order for solar arrays to be feasible for the mission, their total mass needed to fit within the total budget for the mission, which strongly suggested the use of carbon composite facesheets on an aluminum core for the panel structure. While these composite structures are a good functional substitution for the metallic materials they replace, they present unique challenges when interacting with the harsh Jovian space environment. As a composite material, they are composed of more than one material and can show different base properties depending in differing conditions. Looking at the electrical properties, in an Earth-based environment the carbon component of the composite dominates the response of the material to external stimulus. Under these conditions, the structures strongly resembles a conductor. In the Jovian environment, with temperatures reaching 50K and under the bombardment from energetic electrons, the non-conducting pre-preg binding materials may come to the forefront and change the perceived response. Before selecting solar arrays as the baseline power source for a mission to Jupiter, the response of the carbon composites to energetic electrons while held at cryogenic temperatures needed to be determined. A series of tests were devised to exam the response of a sample solar array panel composed of an M55J carbon weave layup with an RS-3 pre-preg binder. Test coupons were fabricated and exposed to electrons ranging from 10 keV to 100 keV, at 1 nA/cm2, while being held at cryogenic temperatures. While under electron bombardment, electrical discharges were observed and recorded with the majority of discharges occurring with electron energies of 25 keV. A decrease in temperature to liquid nitrogen temperatures showed a marked increase in the magnitude of these discharges. The results indicate that dielectric discharges are primarily produced due to the presence of large regions of the non-conductive pre-preg on the surface of the carbon sheets. The frequency and magnitude of discharges decreased when layers of the pre-preg material were removed from the composite surface. These tests indicate that solar array panels may be used in the Jovian environment, but that electrostatic discharges can be expected on the carbon composite solar arrays.

Jupiter↗

DOE OSTI2020

Reshaping of Truncated Pd Nanocubes: Energetic and Kinetic Analysis Integrating Transmission Electron Microscopy with Atomistic-Level and Coarse-Grained Modeling

Stability against reshaping of metallic fcc nanocrystals synthesized with tailored far-from-equilibrium shapes is key to maintaining optimal properties for applications such as catalysis. Yet Arrhenius analysis of experimental reshaping kinetics, and appropriate theory and simulation, is lacking. As such, we use TEM to monitor the reshaping of Pd nanocubes of ~25 nm side length between 410 °C (over ~4.5 h) and 440 °C (over ~0.25 h), extracting a high effective energy barrier of E eff ≈ 4.6 eV. We also provide an analytic determination of the energy variation along the optimal pathway for reshaping that involves transfer of atoms across the nanocube surface from edges or corners to form new layers on side {100} facets. The effective barrier from this analysis is shown to increase strongly with the degree of truncation of edges and corners in the synthesized nanocube. Theory matches experiment for the appropriate degree of truncation. In addition, we perform simulations of a stochastic atomistic-level model incorporating a realistic description of diffusive hopping for undercoordinated surface atoms, thereby providing a visualization of the initial reshaping process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

First-Principles Study of n -Butane Monomolecular Cracking and Dehydrogenation on Two-Dimensional-Zeolite Model Systems: Reaction Mechanisms and Effects of Spatial Confinement

Two-dimensional (2D) ultrathin (~0.5 nm) aluminosilicate bilayer films, consisting of hexagonal prisms (a.k.a. double 6-membered rings D6R) with acidic bridging hydroxyl groups exposed on the surface, have been previously synthesized on a Ru(0001) surface as a zeolite model system. These structures are helpful for mimicking zeolite catalysts with D6R building blocks, such as chabazite. We performed density functional theory calculations to investigate the monomolecular cracking and dehydrogenation of n-butane molecules over the acidic hydroxyl groups of the 2D model system and compared the reaction energetics with that in bulk chabazite. The intrinsic activation energy barrier is the highest for dehydrogenation and lowest for central C–C bond cracking in bulk chabazite. The trend of intrinsic energy barriers for dehydrogenation and terminal and central C–C bond cracking is reproduced on the 2D aluminosilicate film. Overall, the activation barriers are higher on the 2D film than in bulk chabazite due to the lack of confinement in the former. We further explored the effects of the zeolite channel size on the n-butane adsorption and monomolecular cracking using different bulk nanoporous zeolite frameworks (TON, MEL, MEI, and VFI). We found that as the confinement of channels decreases, n-butane adsorption becomes weaker, and the intrinsic energy barrier of terminal C–C cracking increases. The activation energy barriers (dehydrogenation and terminal and central C–C cracking) on the 2D bilayer film surface, which may be considered as zeolite cages at the infinite cage size limit, are close to that in VFI with a relatively large channel size. Comparing the reaction pathway of n-butane terminal C–C cracking in 3D nanocages and on the surface of the 2D aluminosilicate film revealed that stabilizing the transition states in the 3D nanocages is responsible for the decrease in the intrinsic energy barriers for bulk zeolites.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Assessment of the literature about Be-W mixed material layer formation in the fusion reactor environment

Abstract All plasma facing surfaces in a fusion reactor, whether initially pure or an alloy, will rapidly evolve into a mixed material due to plasma-induced erosion, migration and redeposition. Beryllium (Be) erosion from the main chamber, and its transport and deposition on to a tungsten (W) divertor results in the growth of mixed Be-W layers, which can evolve to form beryllides. These Be-W mixed materials exhibit generally less desirable properties than pure tungsten or pure beryllium, such as lower melting points. In order to better understand the parameter space for growth of these alloys, this paper reviews the literature on Be-W mixed material formation experiments—in magnetically confined fusion reactors, in linear plasma test stands, and during thin-film deposition—and on computational modeling of Be-W interactions, as well as briefly assesses the Be-W growth kinetics. We conclude that the following kinetic steps drive the material mixing: adsorption of the implanted/deposited ion on the metal surface; diffusion of the implanted/deposited ion from surface into the bulk, which is accelerated by defects; and loss of deposited material through erosion. Adsorption dominates (or prevents) material mixing in thin-film deposition experiments, whereas diffusion drives material mixing in plasma exposures due to the energetic ion implantation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2024

Assessment of the literature about Be-W mixed material layer formation in the fusion reactor environment

All plasma facing surfaces in a fusion reactor, whether initially pure or an alloy, will rapidly evolve into a mixed material due to plasma-induced erosion, migration and redeposition. Beryllium (Be) erosion from the main chamber, and its transport and deposition on to a tungsten (W) divertor results in the growth of mixed Be-W layers, which can evolve to form beryllides. These Be-W mixed materials exhibit generally less desirable properties than pure tungsten or pure beryllium, such as lower melting points. In order to better understand the parameter space for growth of these alloys, this paper reviews the literature on Be-W mixed material formation experiments—in magnetically confined fusion reactors, in linear plasma test stands, and during thin-film deposition—and on computational modeling of Be-W interactions, as well as briefly assesses the Be-W growth kinetics. We conclude that the following kinetic steps drive the material mixing: adsorption of the implanted/deposited ion on the metal surface; diffusion of the implanted/deposited ion from surface into the bulk, which is accelerated by defects; and loss of deposited material through erosion. Adsorption dominates (or prevents) material mixing in thin-film deposition experiments, whereas diffusion drives material mixing in plasma exposures due to the energetic ion implantation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

NASA NTRS2018

The Possible Contribution of Dielectric Breakdown to Space Weathering on Phobos

The origins of Phobos and Deimos are uncertain; both are so space weathered that their surface compositions are difficult to determine using spectral reflectance measurements. We show how the winter temperatures and associated conditions in the polar regions of Phobos could make the regolith susceptible to space weathering from dielectric breakdown caused by solar energetic particles (SEPs). During SEP events, charged particles accumulate throughout the top ~ 1 mm of the regolith, which has low condukctivity, and create subsurface electric fields that act to dissipate any net buildup of charge. The faster the net charge accumulates, the larger the electric field needed to dissipate it. If the magnitude of the subsurface electric field exceeds ~10 6 V m -1, then dielectric breadkown is likely. This process rapidly dissipates the buildup of charge by vaporizing electrically conducting channels through the regolith. Dielectric breakdown

Space Weathering↗

NASA NTRS2019

Impacts of Space Weather on Climate and Habitability of Terrestrial Type Exoplanets

The current progress in the detection of terrestrial type exoplanets has opened a new avenue in the characterization of exoplanetary atmospheres and in the search for biosignatures of life with the upcoming ground-based and space missions. To specify the conditions favorable for the origin, development and sustainment of life as we know it in other worlds, we need to understand the nature of astrospheric, atmospheric and surface environments of exoplanets in habitable zones around G-K-M dwarfs including our young Sun. Global environment is formed by propagated disturbances from the planet-hosting stars in the form of stellar flares, coronal mass ejections, energetic particles, and winds collectively known as astrospheric space weather. Its characterization will help in understanding how an exoplanetary ecosystem interacts with its host star, as well as in the specification of the physical, chemical and biochemical conditions that can create favorable and/or detrimental conditions for planetary climate and habitability along with evolution of planetary internal dynamics over geological timescales. A key linkage of (astro) physical, chemical, and geological processes can only be understood in the framework of interdisciplinary studies with the incorporation of progress in heliophysics, astrophysics, planetary and Earth sciences. The assessment of the impacts of host stars on the climate and habitability of terrestrial (exo)planets will significantly expand the current definition of the habitable zone to the biogenic zone and provide new observational strategies for searching for signatures of life. The major goal of this paper is to describe and discuss the current status and recent progress in this interdisciplinary field and to provide a new roadmap for the future development of the emerging field of exoplanetary science and astrobiology.

astrophysics↗

DOE OSTI2024

Metadynamics investigation of lanthanide solvation free energy landscapes and insights into separations energetics

Lanthanide ion solvation chemistry in nonaqueous phases is key to understanding and developing effective separation processes for these critical materials. Due to the complexity and inherent disorder of the solution phase, a comprehensive picture of the solvated metal ion is often difficult to generate solely from conventional spectroscopic approaches and electronic structure calculations, particularly in the extractant phase. In this work, we use classical molecular dynamics (MD) simulation with an advanced sampling technique, metadynamics, supplemented by experimental spectroscopy and speciation analysis, to measure lanthanide solvation free energy landscapes. We define coordination-based collective variables to probe the entire range of solvation configurations in the organic phase of lanthanum (La), europium (Eu), and lutetium (Lu) nitrate salts bound with a commonly used extractant, N,N′-dimethyl, N,N′-dioctylhexylethoxymalonamide (DMDOHEMA). The known lanthanide extraction trend of La ≈ Eu > Lu is readily explained by the measured free energy surfaces, which show consistent DMDOHEMA coordination from La to Eu, followed by loss of DMDOHEMA coordination from Eu to Lu. These simulations suggest how ligand crowding at the metal center can control selectivity, in this case resulting in the opposite extraction trend as observed with other conventional extractants, where the enthalpic contribution from increasing lanthanide charge density across the series dominates the extraction energetics. We also find that the presence of inner-sphere water, verified by time-resolved fluorescence, diversifies the accessible solvation structures. As a result, understanding solvation requires consideration of an entire thermodynamic ensemble, rather than the single dominant lowest-energy structure, as is often considered out of necessity in interpretation of spectroscopic data or in electronic structure-based ligand design approaches. In general, we demonstrate how metadynamics uniquely enables investigation of complex, multidimensional solvation energetic landscapes, and how it can explain selectivity trends where extraction is controlled by more complex mechanisms than simple charge density-based selectivity.

Wang, Xiaoyu↗