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At least 973 records · Page 54

Do Ag{sub n} (up to n = 8) clusters retain their identity on graphite? Insights from first-principles calculations including dispersion interactions

Adsorption of pre-formed Ag{sub n} clusters for n = 1 − 8 on a graphite substrate is studied within the density functional theory employing the vdW-DF2 functional to treat dispersion interactions. Top sites above surface layer carbon atoms turn out to be most favorable for a Ag adatom, in agreement with experimental observations. The same feature is observed for clusters of almost all sizes which have the lowest energies when the Ag atoms are positioned over top sites. Most gas phase isomers retain their structures over the substrate, though a couple of them undergo significant distortions. Energetics of the adsorption can be understood in terms of a competition between energy cost of disturbing Ag–Ag bonds in the cluster and energy gain from Ag–C interactions at the surface. Ag{sub 3} turns out to be an exceptional candidate in this regard that undergoes significant structural distortion and has only two of the Ag atoms close to surface C atoms in its lowest energy structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA Tech Briefs, August 2008

Customizable Digital Receivers for Radar Two-Camera Acquisition and Tracking of a Flying Target Visual Data Analysis for Satellites A Data Type for Efficient Representation of Other Data Types Hand-Held Ultrasonic Instrument for Reading Matrix Symbols Broadband Microstrip-to-Coplanar Strip Double-Y Balun A Topographical Lidar System for Terrain-Relative Navigation Programmable Low-Voltage Circuit Breaker and Tester Electronic Switch Arrays for Managing Microbattery Arrays Topics covered include: Lower-Dark-Current, Higher-Blue-Response CMOS Imagers; Fabricating Large-Area Sheets of Single-Layer Graphene by CVD; Support for Diagnosis of Custom Computer Hardware; Providing Goal-Based Autonomy for Commanding a Spacecraft; Dynamic Method for Identifying Collected Sample Mass; Optimal Planning and Problem-Solving; Attitude-Control Algorithm for Minimizing Maneuver Execution Errors; Grants Document-Generation System; Heat-Storage Modules Containing LiNO3 3H2O and Graphite Foam; Precipitation-Strengthened, High-Temperature, High-Force Shape Memory Alloys; Improved Relief Valve Would Be Less Susceptible to Failure; Safety Modification of Cam-and-Groove Hose Coupling; Using Composite Materials in a Cryogenic Pump; Using Electronic Noses to Detect Tumors During Neurosurgery; Producing Newborn Synchronous Mammalian Cells; Smaller, Lower-Power Fast-Neutron Scintillation Detectors; Rotationally Vibrating Electric-Field Mill; Estimating Hardness from the USDC Tool-Bit Temperature Rise; Particle-Charge Spectrometer; Automated Production of Movies on a Cluster of Computers; FIDO-Class Development Rover; and Tone-Based Command of Deep Space Probes Using Ground Antennas.

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Enhancing the inherent catalytic activity and stability of TiO 2 supported Pt single-atoms at CeO x –TiO 2 interfaces

Single-atoms (SAs) with atomically coordinated reaction centers are considered the next generation of catalysts that can exhibit exceptional catalytic efficiency. However, the general concern about thermodynamic vulnerabilities of SAs questions their practical value. Moreover, whether the inherent catalytic nature of SAs is superior compared with that of larger nanoparticles is still under debate. Here, we address two controversies by a comparative study using two catalysts: Pt/TiO 2 and Pt/CeO x –TiO 2 . Based on a hierarchical study of density functional theory, time-resolved catalysis performance test, in situ infrared spectroscopy, and operando X-ray absorption spectroscopy, we could unveil the catalytic nature of Pt-SAs and their stability. By utilizing the heterogeneous interface formed between TiO 2 supporting particles and CeO x clusters formed on the surface of TiO 2 , we preferentially synthesized Pt-SAs pinned at the CeO x –TiO 2 interfaces on CeO x –TiO 2 hybrid-oxide supports. The strong electronic coupling between the Pt-SAs and the Ce ions at the CeO x –TiO 2 interfaces enhanced the catalytic activity toward CO oxidation of Pt-SAs and improved the long-term stability under CO oxidation conditions. The CO oxidation activity of Pt-SAs stabilized at CeO x –TiO 2 was improved by 13.5 times at 200 °C compared with the Pt-SAs on TiO 2 . The results present how to easily improve the activity and stability of Pt-SAs using a simple interface control method. Moreover, we demonstrate that the catalytic activity and the stability of Pt-SAs can be monitored through the chemical state of the interfaces. Finally, our study provides comprehensive understanding about the catalytic nature as well as a novel strategy toward applications of Pt-SAs, enabling sustainable use of Pt in heterogeneous catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemically Determined and Structurally Justified Thermochemistry of H atom Transfer on Ti-Oxo Nodes of the Colloidal Metal–Organic Framework Ti-MIL-125

Titanium dioxide (TiO 2 ) has long been employed as (photo)electrodes for reactions relevant to energy storage and renewable energy synthesis. Proton-coupled electron transfer (PCET) reactions with equimolar amounts of protons and electrons at the TiO 2 surface or within the bulk structure lie at the center of these reactions. Because a proton and an electron are thermochemically equivalent to an H-atom, these reactions are essentially H-atom transfer reactions. Thermodynamics of H-atom transfer has a complex dependence on the synthetic protocol and chemical history of the electrode, the reaction medium, and many others; together, these complications preclude the understanding of the H-atom transfer thermochemistry with atomic-level structural knowledge. Herein, we report our success in employing open-circuit potential (E OCP ) measurements to quantitatively determine the H-atom transfer thermochemistry at structurally well-defined Ti-oxo clusters within a colloidally stabilized metal–organic framework (MOFs), Ti-MIL-125. The free energy to transfer H-atom, Ti 3+ O–H bond dissociation free energy (BDFE), was measured to be 68(2) kcal mol -1 . To the best of our understanding, this is the first report on using E OCP measurements to quantify thermochemistry on any MOFs. The proton topology, the structural change upon the redox reaction, and BDFE values were further quantitatively corroborated using computational simulations. Furthermore, comparisons of the E OCP -derived BDFEs of Ti-MIL-125 to similar parameters in the literature suggest that E OCP should be the preferred method for quantitatively accurate BDFE calculations. Here, the reported success in employing E OCP for nanosized Ti- MIL-125 should lay the ground for thermochemical measurements of other colloidal systems, which are otherwise challenging. Implications of these measurements on Ti-MIL-125 as an H-atom acceptor in chemical reactions and comparisons with other MOFs/metal oxides are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding the hydrological response of a headwater-dominated catchment by analysis of distributed surface–subsurface interactions

Abstract We computationally explore the relationship between surface–subsurface exchange and hydrological response in a headwater-dominated high elevation, mountainous catchment in East River Watershed, Colorado, USA. In order to isolate the effect of surface–subsurface exchange on the hydrological response, we compare three model variations that differ only in soil permeability. Traditional methods of hydrograph analysis that have been developed for headwater catchments may fail to properly characterize catchments, where catchment response is tightly coupled to headwater inflow. Analyzing the spatially distributed hydrological response of such catchments gives additional information on the catchment functioning. Thus, we compute hydrographs, hydrological indices, and spatio-temporal distributions of hydrological variables. The indices and distributions are then linked to the hydrograph at the outlet of the catchment. Our results show that changes in the surface–subsurface exchange fluxes trigger different flow regimes, connectivity dynamics, and runoff generation mechanisms inside the catchment, and hence, affect the distributed hydrological response. Further, changes in surface–subsurface exchange rates lead to a nonlinear change in the degree of connectivity—quantified through the number of disconnected clusters of ponding water—in the catchment. Although the runoff formation in the catchment changes significantly, these changes do not significantly alter the aggregated streamflow hydrograph. This hints at a crucial gap in our ability to infer catchment function from aggregated signatures. We show that while these changes in distributed hydrological response may not always be observable through aggregated hydrological signatures, they can be quantified through the use of indices of connectivity.

54 ENVIRONMENTAL SCIENCES↗

Assessing electronic structure approaches for gas-ligand interactions in metal-organic frameworks: The CO{sub 2}-benzene complex

Adsorption of gas molecules in metal-organic frameworks is governed by many factors, the most dominant of which are the interaction of the gas with open metal sites, and the interaction of the gas with the ligands. Herein, we examine the latter class of interaction in the context of CO{sub 2} binding to benzene. We begin by clarifying the geometry of the CO{sub 2}–benzene complex. We then generate a benchmark binding curve using a coupled-cluster approach with single, double, and perturbative triple excitations [CCSD(T)] at the complete basis set (CBS) limit. Against this ΔCCSD(T)/CBS standard, we evaluate a plethora of electronic structure approximations: Hartree-Fock, second-order Møller-Plesset perturbation theory (MP2) with the resolution-of-the-identity approximation, attenuated MP2, and a number of density functionals with and without different empirical and nonempirical van der Waals corrections. We find that finite-basis MP2 significantly overbinds the complex. On the other hand, even the simplest empirical correction to standard density functionals is sufficient to bring the binding energies to well within 1 kJ/mol of the benchmark, corresponding to an error of less than 10%; PBE-D in particular performs well. Methods that explicitly include nonlocal correlation kernels, such as VV10, vdW-DF2, and ωB97X-V, perform with similar accuracy for this system, as do ωB97X and M06-L.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

BH-DFTB/DFT calculations for iron clusters

We present a study on the structural, electronic, and magnetic properties of Fe{sub n}(n = 2 − 20) clusters by performing density functional tight binding (DFTB) calculations within a basin hopping (BH) global optimization search followed by density functional theory (DFT) investigations. The structures, total energies and total spin magnetic moments are calculated and compared with previously reported theoretical and experimental results. Two basis sets SDD with ECP and 6-31G** are employed in the DFT calculations together with BLYP GGA exchange-correlation functional. The results indicate that the offered BH-DFTB/DFT strategy collects all the global minima of which different minima have been reported in the previous studies by different groups. Small Fe clusters have three kinds of packing; icosahedral (Fe{sub 9−13}), centered hexagonal antiprism (Fe{sub 14−17}, Fe{sub 20}), and truncated decahedral (Fe{sub 17(2)}, Fe{sub 18−19}). It is obtained in a qualitative agreement with the time of flight mass spectra that the magic numbers for the small Fe clusters are 7, 13, 15, and 19 and with the collision induced dissociation experiments that the sizes 6, 7, 13, 15, and 19 are thermodynamically more stable than their neighboring sizes. The spin magnetic moment per atom of Fe{sub n}(n = 2 − 20) clusters is between 2.4 and 3.6 μ{sub B} for the most of the sizes. The antiferromagnetic coupling between the central and the surface atoms of the Fe{sub 13} icosahedron, which have already been reported by experimental and theoretical studies, is verified by our calculations as well. The quantitative disagreements between the calculations and measurements of the magnetic moments of the individual sizes are still to be resolved.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Development of a three-dimensional APOLLO3 neutrons deterministic scheme for the CABRI reactor

CABRI is an experimental reactor to study the fuel behavior during reactivity injection transients. These transients being highly multiphysics, the development of suitable modeling and simulation tools to simulate them is important for the optimization of the tests and the control of the experimental conditions. This paper focuses on the development of an APOLLO3 deterministic core calculation tool dedicated to the CABRI transient analysis. It represents the first stage of the incremental process for the implementation of a multiphysics time-dependent modeling of the CABRI transient. The neutron calculation scheme is based on a classical two-step approach. The first step consists of a 281-energy group calculation flux with the TDT-MOC (Method Of Characteristics) solver for cross-section space and energy (23 groups) collapsing for the CABRI different assembly clusters. The bias on a 2D core neutron calculation due to the self-shielding calculation and collapsing on a restricted pattern are investigated thanks to a comparison with a direct full 2D calculation on a quarter of core. The second step relies on a pin-resolved transport 3D transport core calculation with the SN solver MINARET. A progressive numerical validation process is followed to quantify the calculation biases on reactivity and reaction rates at each step using reference calculations with the stochastic code TRIPOLI4. The next development stage toward a multiphysics scheme will be the implementation of the 3D-kinetics equation resolution and the coupling with a core thermal-hydraulics model. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Seniority zero pair coupled cluster doubles theory

Coupled cluster theory with single and double excitations accurately describes weak electron correlation but is known to fail in cases of strong static correlation. Fascinatingly, however, pair coupled cluster doubles (p-CCD), a simplified version of the theory limited to pair excitations that preserve the seniority of the reference determinant (i.e., the number of unpaired electrons), has mean field computational cost and is an excellent approximation to the full configuration interaction (FCI) of the paired space provided that the orbital basis defining the pairing scheme is adequately optimized. In previous work, we have shown that optimization of the pairing scheme in the seniority zero FCI leads to a very accurate description of static correlation. The same conclusion extends to p-CCD if the orbitals are optimized to make the p-CCD energy stationary. We here demonstrate these results with numerous examples. We also explore the contributions of different seniority sectors to the coupled cluster doubles (CCD) correlation energy using different orbital bases. We consider both Hartree-Fock and Brueckner orbitals, and the role of orbital localization. We show how one can pair the orbitals so that the role of the Brueckner orbitals at the CCD level is retained at the p-CCD level. Moreover, we explore ways of extending CCD to accurately describe strongly correlated systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Facile synthesis of QD-anchored composite particles with magnetite cluster cores ({sup n}Fe{sub 3}O{sub 4}@SiO{sub 2}@QDs)

Highlights: ► Triple layered Fe{sub 3}O{sub 4}/SiO{sub 2}/QDs were designed as fluorescent magnetic nanocomposites. ► Magnetite cluster-embedded silica exhibited strong and controllable magnetism. ► Effective conjugation between QDs and magnetic silica occurred at pH3. - Abstract: Magnetism-controlled fluorescent composite particles ({sup n}Fe{sub 3}O{sub 4}@SiO{sub 2}@QDs) were prepared as QD-anchored silica nanoparticles with magnetite cluster cores. First, citrate-capped magnetites (C-Fe{sub 3}O{sub 4}) were prepared by the co-precipitation method and subsequently complexed with 3-aminopropyl-trimethoxysilane (APTMS) at room temperature, consequently leading to the formation of magnetite clusters (A-{sup n}Fe{sub 3}O{sub 4}) with alkoxy terminated interfaces. The sol–gel reaction between A-{sup n}Fe{sub 3}O{sub 4} and tetraethoxysilane (TEOS) produced the core-shell {sup n}Fe{sub 3}O{sub 4}@SiO{sub 2}. The resulting core-shell particles exhibited superparamagnetic properties and controllable magnetism simply by adjusting the thickness of nonmagnetic silica layer. After then, amine-terminated {sup n}Fe{sub 3}O{sub 4}@SiO{sub 2} (NH{sub 2}–{sup n}Fe{sub 3}O{sub 4}@SiO{sub 2}) was conjugated with carboxy quantum dots (QDs) using an EDC coupling agent. The QD conjugation with NH{sub 2}–{sup n}Fe{sub 3}O{sub 4}@SiO{sub 2} of lower pH exhibited the higher photoluminescence (PL) intensity, and the resulting composite particles ({sup n}Fe{sub 3}O{sub 4}@SiO{sub 2}@QDs) can be a useful biomedical agent. This chemical strategy can be further applied to prepare the core-shell magnetic nanostructure with various oxide layers for specific applications.

36 MATERIALS SCIENCE↗

Development of mathematical model and simulation tool for the high capacity production of carbon fiber

Weight reduction in the transportation is the most effective way for reducing fuel consumption. Carbon fiber composites have been increasingly used by automotive manufacturers in vehicle nonstructural and structural parts. Larger penetration of carbon fiber-based materials requires very large quantities of fiber at a low price, and of consistently high quality. The advancements in carbon fiber technology that are required to achieve this production scale-up and cost reduction, are very challenging. The most expensive production step is the conversion of textile-grade polyacrylonitrile (PAN) precursor to carbon fiber. The conversion takes place in three main stages: stabilization, low and high temperature carbonization. Most of the research to date has focused on the stabilization of the PAN precursors and oxidized PAN fibers. Comparingly little effort has been dedicated to the investigation of processing conditions during low temperature (LT) carbonization. During this stage of fiber conversion, the largest fiber mass loss occurs, and the fundamental carbon fiber structure and material properties are established. The understanding of the conversion processes in the LT furnace, and the effects of spatial and temporal variations of the LT process parameters on the carbon fiber properties are necessary to identify possible process improvements and cost savings. The objective of this research was to develop computational models for gas flow and energy transport in the gas and fiber phases of the LT furnace, and to couple them with the fiber conversion process models. The model is implemented in the three-dimensional framework that enables analysis of process condition variations in all directions. The formulation is based on modified transport equation to simulate steady state conditions and thus significantly reduce computational effort associated with transient methods. The model is implemented in open source computational fluid dynamics (CFD) code OpenFOAM. The model has been demonstrated on a prototype carbon fiber LT furnace and can be extended to other geometries and process conditions. Extensions to other physical effects, such as accounting evolution of multiple gas species, and fiber tensioning are straightforward. The model uses High Performance Computing (HPC) capabilities of OpenFOAM and can be implemented on multi-processor workstations or mid-size computer clusters common in the industrial setting.

36 MATERIALS SCIENCE↗

Joint Management and Optimization of Residential Natural Gas and Electricity Distribution Networks Coupled via Fuel Cells

The interesting properties of natural gas as well as the growing electric power demand worldwide have led to increasing attention to natural-gas-based distributed generation applications in electric distribution systems. This paper goes over the interdependency between a residential natural gas network and an electric distribution network that are coupled via fuel cells. The modeling of the gas network is introduced first, and then the algorithm for gas flow study is presented. The optimal placement and sizing of fuel cell based distributed generation systems are formulated to minimize the losses in both the gas and electric distribution networks, subject to their model constraints. In addition to this, in order to capture the probabilistic nature of the optimization problem under study, the K-means clustering algorithm is applied to the gas and electricity demands to determine hourly load states and their corresponding probabilities. Furthermore, simulation studies are carried out on an integrated system consisting of the IEEE 69-bus distribution feeder and a radial 27-node natural gas network to verify the developed optimization model and the proposed method.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Room-temperature ferromagnetism of Fe-doped TiO{sub 2} nanoparticles driven by oxygen vacancy

Graphical abstract: A series of Ti{sub 1−x}Fe{sub x}O{sub 2−δ} (x ≤ 0.03) nanoparticles (NPs) were synthesized by sol–gel route. The room temperature ferromagnetism (RTFM) has been explained in terms of vacancy induced bound magnetic polaron (BMP) model, where the Fe{sup 3+} ions ferromagnetically coupled mediated by oxygen vacancies. Display Omitted Highlights: ► The Fe-doped NPs have been synthesized by sol–gel method. ► Ferromagnetism of Fe-doped TiO{sub 2} NPs are intrinsic property. ► Room temperature ferromagnetism observed in all the Fe-doped samples. ► Variation in M{sub s} is attributed due to oxygen vacancies and defect formation. -- Abstract: A series of Ti{sub 1−x}Fe{sub x}O{sub 2−δ} (0 ≤ x ≤ 0.03) nanoparticles (NPs) were synthesized by sol–gel route. The NPs had a size distribution in the range of 15–40 nm and were identified as the anatase TiO{sub 2} by X-ray diffraction (XRD) and Raman analysis. XRD, selected area electron diffraction, Raman and Mössbauer analysis ruled out the signature of Fe-cluster or any other oxides of Fe. The redshifting of the band edge emission peak observed in UV–vis absorption studies further confirmed the doping of Fe ions in the TiO{sub 2} lattice. Raman studies show the shifting and broadening in E{sub g}(1) and E{sub g}(3) modes with Fe doping. It suggested that the activation of ferromagnetism with increasing Fe doping concentration was related to the oxygen vacancy defects. The presence of such defects was further confirmed from electron paramagnetic resonance (EPR) measurements. The observed ferromagnetism is interpreted in terms of bound magnetic polaron (BMP) model.

36 MATERIALS SCIENCE↗

Multireference linearized coupled cluster theory for strongly correlated systems using matrix product states

We propose a multireference linearized coupled cluster theory using matrix product states (MPSs-LCC) which provides remarkably accurate ground-state energies, at a computational cost that has the same scaling as multireference configuration interaction singles and doubles, for a wide variety of electronic Hamiltonians. These range from first-row dimers at equilibrium and stretched geometries to highly multireference systems such as the chromium dimer and lattice models such as periodic two-dimensional 1-band and 3-band Hubbard models. The MPS-LCC theory shows a speed up of several orders of magnitude over the usual Density Matrix Renormalization Group (DMRG) algorithm while delivering energies in excellent agreement with converged DMRG calculations. Also, in all the benchmark calculations presented here, MPS-LCC outperformed the commonly used multi-reference quantum chemistry methods in some cases giving energies in excess of an order of magnitude more accurate. As a size-extensive method that can treat large active spaces, MPS-LCC opens up the use of multireference quantum chemical techniques in strongly correlated ab initio Hamiltonians, including two- and three-dimensional solids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Performance of an atomic mean-field spin–orbit approach within exact two-component theory for perturbative treatment of spin–orbit coupling

The paper reports development of an atomic mean-field (AMF) spin–orbit approach within the spin-free exact two-component theory in its one-electron variant (SFX2C-1e), a new relativistic quantum-chemical method for treating spin-orbit coupling in molecules. The effective one-electron spin–orbit integral matrix in the four-component representation is assembled as a direct sum of one-centre spin–orbit integral matrices with the mean-field two-electron contributions evaluated using atomic SFX2C-1e Hartree–Fock density matrices. It is then transformed into two-component representation using analytic SFX2C-1e energy derivative formulation. The resulting two-component spin–orbit integral matrix is by design suitable for use in perturbative calculations of spin–orbit coupling, treating SFX2C-1e wavefunctions as unperturbed states. The accuracy of the present AMF approach has been demonstrated using benchmark calculations of spin–orbit splittings for representative diatomic radicals at the equation-of-motion coupled-cluster singles and doubles level. In conclusion, to demonstrate the applicability and accuracy of the present perturbative spin–orbit scheme in calculations of challenging heavy-element containing systems, a thorough computational investigation of six low-lying electronic states of ThO+ is reported.

74 ATOMIC AND MOLECULAR PHYSICS↗

Cluster Analysis of IRIS Spectroscopic Line Profiles and SDO/AIA EUV Emission in Observations and RMHD Simulations of the Solar Atmosphere

Spatially-resolved observations from the IRIS and SDO/AIA satellites, especially when coupled with realistic 3D RMHD simulations, are a powerful tool for analysis of processes in the solar chromosphere, transition region, and corona. However, the complexity of the data makes understanding the observations and modeling results difficult. In this work, we apply unsupervised clustering algorithms for analysis of observational and synthetic chromospheric Mg II h&k 2796Å&2803Å and transition region C II 1334Å&1335Å line profiles observed by IRIS, and extreme ultraviolet (EUV) emission observed by SDO/AIA, for various types of problems. The synthetic line profiles are computed for simulations of the quiescent solar atmosphere (using the StellarBox and RH1.5 codes). The K-Means clustering algorithm is applied, and the selection of an optimal number of clusters is supported by the average silhouette width technique. We discuss applications of the line profile clustering method to 1) visualization of computational and observational spectroscopic imaging data; 2) understanding of evolutionary trends and behavior patterns of quiet Sun emission and during solar flares; and 3) recognition of heating events and shock waves.

Sadykov, Viacheslav↗

Solvothermal Synthesis of [Cr 7 S 8 (en) 8 Cl 2 ]Cl 3 ⋅ 2H 2 O with Magnetically Frustrated [Cr 7 S 8 ] 5+ Double‐Cubes**

Abstract A novel transition metal chalcohalide [Cr 7 S 8 (en) 8 Cl 2 ]Cl 3 ⋅ 2H 2 O, with [Cr 7 S 8 ] 5+ dicubane cationic clusters, has been synthesized by a low temperature solvothermal method, using dimethyl sulfoxide (DMSO) and ethylenediamine ( en ) solvents. Ethylenediamine ligand exhibits bi‐ and monodentate coordination modes; in the latter case ethylenediamine coordinates to Cr atoms of adjacent clusters, giving rise to a 2D polymeric structure. Although magnetic susceptibility shows no magnetic ordering down to 1.8 K, a highly negative Weiss constant, θ =−224(2) K, obtained from Curie‐Weiss fit of inverse susceptibility, suggests strong antiferromagnetic (AFM) interactions between S =3/2 Cr(III) centers. Due to the complexity of the system with (2 S +1) 7 =16384 microstates from seven Cr 3+ centers, a simplified model with only two exchange constants was used for simulations. Density‐functional theory (DFT) calculations yielded the two exchange constants to be J 1 =−21.4 cm −1 and J 2 =−30.2 cm −1 , confirming competing AFM coupling between the shared Cr 3+ center and the peripheral Cr 3+ ions of the dicubane cluster. The best simulation of the experimental data was obtained with J 1 =−20.0 cm −1 and J 2 =−21.0 cm −1 , in agreement with the slightly stronger AFM exchange within the triangles of the peripheral Cr 3+ ions as compared to the AFM exchange between the central and peripheral Cr 3+ ions. This compound is proposed as a synthon towards magnetically frustrated systems assembled by linking dicubane transition metal‐chalcogenide clusters into polymeric networks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Machine learning to discover mineral trapping signatures due to CO 2 injection

Mineral trapping is pursued as a geological CO 2 sequestration (GCS) mechanism because it permanently stores CO 2 in solid phases or minerals. However, CO 2 mineral-trapping mechanisms are poorly understood due to (1) lack of sufficient field and laboratory data characterizing these complex processes, and (2) challenges to develop site-specific reactive-transport models coupling fluid flow and geochemical reactions occurring at various temporal (from milliseconds to years) and spatial (from pore (millimeters) to field (kilometers)) scales. Reactive transport with additional complexities such as heterogeneity can make the simulation outputs even more difficult to interpret because of complex nonlinearity and multi-scale interdependencies. Furthermore, the values of model outputs such as concentrations can vary by several orders of magnitude, making it harder to correlate and characterize the impact of the variables via traditional data interpretation techniques such as exploratory data analyses. Recently, machine learning (ML) has shown promise in feature discovery and in highlighting hidden mechanisms that cannot be obtained by existing data-analytics and statistical methods. In this study, we applied an unsupervised ML approach, non-negative matrix factorization with custom -means clustering (NMF) to the data generated by reactive-transport simulations of GCS. The reactive-transport data consisted of 19 attributes, including four physio-chemical variables (pH, porosity, aqueous CO 2 , and sequestered CO 2 ), six chemical species (K + , Na + , HCO, Ca 2+ , Mg 2+ , Fe 2+ ), and four carbonate minerals (calcite, dolomite, siderite, and ankerite), a feldspar mineral (albite), and four clay minerals (illite, clinochlore, kaolinite, and smectite) over a period of 200 years of simulation time. Furthermore, the simulation data used was for Morrow B sandstone at the Farnsworth hydrocarbon unit in Texas. Data are sampled at two locations within the model domain: (1) at the injection well and (2) 200 m west of the injection well. The injection was performed for a period of 10 years. Using NMF, we estimated the temporal interdependencies among the 19 attributes over a span of 200 years. We found that NMF was able to identify four reaction stages and their dominant attributes; these cannot be directly discerned through traditional visualization (e.g., line plots, Pareto analysis, Glyph-based visualization methods) or exploratory data analysis tools of the simulation data. The four stages were: reactions in the injection phase followed by short-, mid-, and long-term reactions. The NMF analysis also revealed that 10 among the 19 attributes are dominant. These dominant attributes for mineral trapping include calcite, dolomite at injection well, siderite at 200 m away from the injection well, clinochlore, kaolinite, Na + , K + , Ca 2+ , Mg 2+ , pH, and aqeuous CO 2 . Finally, at late times (65–200 years), our results showed that calcite plays a major role in mineral trapping with insignificant contribution from siderite, ankerite, and clay minerals. These findings make the proposed unsupervised ML-model attractive for reactive-transport sensing towards real-time GCS monitoring.

54 ENVIRONMENTAL SCIENCES↗