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DOE OSTI2021

Modeling dissociation of ionic liquids with electrolyte NRTL model

Dissociation of ionic liquids (ILs) is critical to electrochemical process performance by affecting ionic conductivity. Prior studies of thermodynamic modeling either assumed no dissociation or complete dissociation that were not consistent with experimental observations. This work presented an eNRTL model for three aqueous imidazolium-based IL systems: [Emim][EtSO 4 ], [Emim][TFA], and [Emim][TfO]. The model accurately correlates the IL dissociation and VLE data in the entire concentration range from pure IL to infinite dilution aqueous solution. The system non-ideality is dominated by the dissociation chemistry. Dissociation behavior is driven by strong short-range interaction of the molecular IL-water pair relative to the dissociated IL-water pair, consistent with prior studies indicating that molecular IL and water can form an energetically favorable complex. The interaction energy parameters calculated in this work qualitatively agrees with the hydrogen bonding ability of the anions previously reported. This research not only provides a model that well describes the IL dissociation but also demonstrates the physical significance of eNRTL model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2004

Theoretical Investigation of OCN(-) Charge Transfer Complexes in Condensed Phase Media: Spectroscopic Properties in Amorphous Ice

Density functional theory (DFT) calculations of cyanate (OCN(-)) charge-transfer complexes were performed to model the "XCN" feature observed in interstellar icy grain mantles. OCN(-) charge-transfer complexes were formed from precursor combinations of HNCO or HOCN with either NH3 or H2O. Three different solvation strategies for realistically modeling the ice matrix environment were explored, including (1) continuum solvation, (2) pure DFT cluster calculations, and (3) an ONIOM DFT/PM3 cluster calculation. The model complexes were evaluated by their ability to reproduce seven spectroscopic measurements associated with XCN: the band origin of the OCN(-) asymmetric stretching mode, shifts in that frequency due to isotopic substitutions of C, N, O, and H, plus two weak features. The continuum solvent field method produced results consistent with some of the experimental data but failed to account for other behavior due to its limited capacity to describe molecular interactions with solvent. DFT cluster calculations successfully reproduced the available spectroscopic measurements very well. In particular, the deuterium shift showed excellent agreement in complexes where OCN(-) was fully solvated. Detailed studies of representative complexes including from two to twelve water molecules allowed the exploration of various possible solvation structures and provided insights into solvation trends. Moreover, complexes arising from cyanic or isocyanic acid in pure water suggested an alternative mechanism for the formation of OCN(-) charge-transfer complexes without the need for a strong base such as NH3 to be present. An extended ONIOM (B3LYP/PM3) cluster calculation was also performed to assess the impact of a more realistic environment on HNCO dissociation in pure water.

Park, Jin-Young↗

DOE OSTI2022

Analysis of short‐ and long‐term system response during gas production from a gas hydrate deposit at the UBGH2‐6 site of the Ulleung Basin in the Korean East Sea

Abstract This study is a continuation of an investigation into the feasibility of long‐term production from a marine hydrate accumulation that has the properties and conditions of the UBGH2‐6 (UBGH2, Ulleung Basin Gas Hydrates 2; 2 is the number of the scientific expedition) site at the Ulleung Basin in the Korean East Sea. The 12.7 m‐thick system is in deep water (2157 m), but at 140 m below the seafloor. It is characterized by alternating hydrate‐free clays and muds and hydrate‐rich sand layers. The layered stratigraphy and the presence of mud layers favours the use of vertical wells rather than horizontal wells for production. The analysis indicates that production from such a hydrate accumulation is technically feasible, but the gas production rates are generally low. Water production accompanying gas production from this deposit appears manageable under all the scenarios investigated in this study, however, the water‐to‐gas ratio is high. Subsidence at the ocean floor at the end of a 14 day test is quite limited. However, there is significant uncertainty in the predictions of the geomechanical system's behaviour because they are not based on measured system properties but only on estimates/assumptions from analogues. The long‐term production potential of the reservoir at the site investigated here appears challenging because of the limited effectiveness of dissociation and large water production, in addition to substantial subsidence.

Moridis, George J.↗

DOE OSTI2023

Activation and Conversion of Methane to Syngas over ZrO 2 /Cu(111) Catalysts near Room Temperature

Enzymatic systems achieve the catalytic conversion of methane at room temperature under mild conditions. Here, in this study, varying thermodynamic and kinetic parameters, we show that the reforming of methane by water (MWR, CH 4 + H 2 O → CO + 3H 2 ) and the water-gas shift reaction (WGS, CO + H 2 O → H 2 + CO 2 ), two essential processes to integrate fossil fuels toward a H2 energy loop, can be achieved on ZrO 2 /Cu(111) catalysts near room temperature. Measurements of ambient-pressure X-ray photoelectron spectroscopy and mass spectrometry, combined with density functional calculations and kinetic Monte Carlo simulations, were used to study the behavior of the inverse oxide/metal catalysts. The superior performance is associated with a unique zirconia-copper interface, where multifunctional sites involving zirconium, oxygen, and copper work coordinatively to dissociate methane and water at 300 K and move forward the MWR and WGS processes.

03 NATURAL GAS↗

DOE OSTI2022

Hydration-driven stabilization and volume collapse of grain boundaries in Mg2SiO4 forsterite predicted by first-principles simulations

Grain boundaries in mantle minerals are of critical importance to geophysical and geochemical processes of the Earth’s interior. One of the fundamental issues is to understand how the water (H 2 O) component influences the properties of grain boundaries in silicate materials. Here, we report the results of the structure and stability of several tilt grain boundaries in Mg 2 SiO 4 forsterite over the pressure range 0 to 15 GPa using density functional theory-based first-principles simulations. Here, the results suggest greater energetic stability and hydration-driven volume collapse (negative excess volume) at zero pressure for the majority of hydrous grain boundaries relative to the anhydrous (dry) ones. All the hydrous grain boundaries become increasingly favorable at elevated pressures as the calculated hydration enthalpy systematically decreases with increasing pressure. The hydrous components at the interfacial regions are predominantly in the hydroxyl form and, to a lesser extent, in the molecular H 2 O form. Their calculated ratio ranges from 1.6 to 8.7 among the different grain boundary configurations. Our structural analysis also reveals that the hydroxyls are bound to either both Mg and Si or to Mg only. In comparison, the molecular species are bound only to Mg sites. Besides direct oxygen-hydrogen bonding, intermolecular hydrogen bonding becomes important with compression. On the basis of our results, we suggest that local atomic rearrangements caused by dissociative adsorption of water facilitate efficient compaction of the boundary interfaces, which, in turn, results in greater relative stability of hydrous grain boundaries. This means that water prefers to be incorporated within the grain boundaries over the bulk of silicate materials.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2019

First-Principles Calculation of Water p K a Using the Newly Developed SCAN Functional

Acid/base chemistry is an intriguing topic that still constitutes a challenge for computational chemistry. While estimating the acid dissociation constant (or pK a ) could shed light on many chemistry processes, especially in the fields of biochemistry and geochemistry, evaluating the relative stability between protonated and nonprotonated species is often very difficult. Indeed, a prerequisite for calculating the pK a of any molecule is an accurate description of the energetics of water dissociation. In this study, we applied constrained molecular dynamics simulations, a noncanonical sampling technique, to investigate the water deprotonation process by selecting the OH distance as the reaction coordinate. The calculation is based on density functional theory and the newly developed SCAN functional, which has shown excellent performance in describing water structure. This first benchmark of SCAN on a chemical reaction shows that this functional accurately models the energetics of proton transfer reactions in an aqueous environment. After taking Coulomb long-range corrections and nuclear quantum effects into account, the estimated water pK a is only 1.0 pK a unit different from the target experimental value. Our results show that the combination of SCAN and constrained MD successfully reproduces the chemistry of water and constitutes a good framework for calculating the free energy of chemical reactions of interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Understanding initial zeolite oligomerization steps with first principles calculations

Zeolites are porous aluminosilicate materials that find various applications in the chemical industry in separations, catalysis, ion exchange, and so forth. However, despite their widespread use, the reaction mechanisms occurring during zeolite growth are still unclear. In the study, we use density functional theory calculations to gain insights into the thermodynamics of oligomerization, which constitute the initial steps of zeolite growth. By taking into consideration solvent and temperature effects, our results demonstrate that the growth of aluminosilicate systems is significantly more exothermic than their pure silicate counterparts. Under pH neutral conditions, water prefers to dissociate on the early-growth-stage aluminosilicate complexes rather than desorb, thus generating potential Brønsted acid sites on the oligomers. Additionally, (alumino)silicate growth pathways are evaluated in the presence of Na + cation, as well as the Ca 2+ cation for the pure silicate pathway. The presence of cations increases the exothermicity of growth, with Ca 2+ exhibiting the most energetically favorable growth environment for the silicate systems. Importantly, we demonstrate through reaction extent analysis that the presence of cations modulates the speciation of the formed oligomers, with Na + favoring linear species in addition to the generally preferred cyclic ones. Overall, this work provides a fundamental understanding of the thermodynamics of complex reaction paths that occur during early stages of zeolite growth and suggests that the initial growth steps can have significant impact on the final zeolite structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Parabolic oxidation kinetics of a plutonium alloy at room temperature

Auger electron spectroscopy (AES) was used to characterize the oxide scale formed on an ~0.5 wt. % Ga plutonium metal alloy. Analysis of changes to the characteristic Auger transitions for Pu and O during sputter depth profiles were used in combination with previously measured sputter yields to determine the thickness of the oxide scale and provide insight into its chemistry. From this data, the parabolic kinetics for the Pu-Ga alloy were determined as a function of relative humidity, RH = 14–92%, and oxygen partial pressure, p(O 2 ) = 31–157 Torr, at 25°C. For each relative humidity investigated, the parabolic rate constant was found to be independent of oxygen partial pressure. Furthermore, power-law fits to the relative humidity effect on the rate constant was found to have a power of n = 1.265, indicating the diffusion species which rate-limits the reaction isn’t molecular water, which subsequent dissociates at the oxide-metal interface, or hydroxyl from dissociation at the gas-surface interface.

36 MATERIALS SCIENCE↗

DOE OSTI2021

High-level coupled-cluster energetics by Monte Carlo sampling and moment expansions: Further details and comparisons

We recently proposed a novel approach to converging electronic energies equivalent to high-level coupled-cluster (CC) computations by combining the deterministic CC(P;Q) formalism with the stochastic configuration interaction (CI) and CC Quantum Monte Carlo (QMC) propagations. This article extends our initial study [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017)], which focused on recovering the energies obtained with the CC method with singles, doubles, and triples (CCSDT) using the information extracted from full CI QMC and CCSDT-MC, to the CIQMC approaches truncated at triples and quadruples. It also reports our first semi-stochastic CC(P;Q) calculations aimed at converging the energies that correspond to the CC method with singles, doubles, triples, and quadruples (CCSDTQ). The ability of the semi-stochastic CC(P;Q) formalism to recover the CCSDT and CCSDTQ energies, even when electronic quasi-degeneracies and triply and quadruply excited clusters become substantial, is illustrated by a few numerical examples, including the F–F bond breaking in F 2 , the automerization of cyclobutadiene, and the double dissociation of the water molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Molecular-orbital-based machine learning for open-shell and multi-reference systems with kernel addition Gaussian process regression

We introduce a novel machine learning strategy, kernel addition Gaussian process regression (KA-GPR), in molecular-orbital-based machine learning (MOB-ML) to learn the total correlation energies of general electronic structure theories for closed- and open-shell systems by introducing a machine learning strategy. The learning efficiency of MOB-ML(KA-GPR) is the same as the original MOB-ML method for the smallest criegee molecule, which is a closed-shell molecule with multi-reference characters. In addition, the prediction accuracies of different small free radicals could reach the chemical accuracy of 1 kcal/mol by training on one example structure. Accurate potential energy surfaces for the H10 chain (closed-shell) and water OH bond dissociation (open-shell) could also be generated by MOB-ML(KA-GPR). To explore the breadth of chemical systems that KA-GPR can describe, we further apply MOB-ML to accurately predict the large benchmark datasets for closed- (QM9, QM7b-T, and GDB-13-T) and open-shell (QMSpin) molecules.

Chemistry↗

DOE OSTI2022

A reaction mechanism for plasma electrolysis of AgNO 3 forming silver nanoclusters and nanoparticles

In plasma-driven solution electrolysis (PDSE), gas-phase plasma-produced species interact with an electrolytic solution to produce, for example, nanoparticles. An atmospheric pressure plasma jet (APPJ) directed onto a liquid solution containing a metallic salt will promote reduction of metallic ions in solution, generating metallic clusters that nucleate to form nanoparticles. In this article, results from a computational investigation are discussed of a PDSE process in which a radio-frequency APPJ sustained in helium impinges on a silver nitrate solution, resulting in growth of silver nanoparticles. A reaction mechanism was developed and implemented in a global plasma chemistry model to predict nanoparticle growth. To develop the reaction mechanism, density functional theory was used to generate probable silver growth pathways up to Ag 9 . Neutral clusters larger than Ag 9 were classified as nanoparticles. Kinetic reaction rate coefficients for thermodynamically favorable growth pathways were estimated based on an existing, empirically determined base reaction mechanism for smaller Ag particle interactions. These rates were used in conjunction with diffusion-controlled reaction rate coefficients that were calculated for other Ag species. The role of anions in reduction of Agn ions in forming nanoparticles is also discussed. Oxygen containing impurities or admixtures to the helium, air entrainment into the APPJ, and dissociation of saturated water vapor above the solution can produce additional reactive oxygen species in solution, resulting in the production of anions and O 2 – in particular. For a given molarity, delivering a sufficient fluence of reducing species will produce similar nanoparticle densities and sizes for all applied power levels. In conclusion, comparisons are made to alternate models for nanoparticle formation, including charged nanoparticles and use of direct current plasmas.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Equation-of-motion internally contracted multireference unitary coupled-cluster theory

The accurate computation of excited states remains a challenge in electronic structure theory, especially for systems with a ground state that requires a multireference treatment. In this work, we introduce a novel equation-of-motion (EOM) extension of the internally contracted multireference unitary coupled-cluster framework (ic-MRUCC), termed EOM-ic-MRUCC. EOM-ic-MRUCC follows the transform-then-diagonalize approach, in analogy to its non-unitary counterpart. By employing a projective approach to optimize the ground state, the method retains additive separability and proper scaling with system size. We show that excitation energies are size-intensive if the EOM operator satisfies the “killer” and the projective conditions. Furthermore, we propose to represent changes in the reference state upon electron excitation via projected many-body operators that span the active orbitals and show that the EOM equations formulated in this way are invariant with respect to active orbital rotations. We test the EOM-ic-MRUCC method truncated to single and double excitations by computing the potential energy curves for several excited states of a BeH2 model system, the HF molecule, and water undergoing symmetric dissociation. Across these systems, our method delivers accurate excitation energies and potential energy curves within 5 mE h (∼0.14 eV) from full configuration interaction. Here, we find that truncating the Baker–Campbell–Hausdorff series to fourfold commutators contributes negligible errors (on the order of 10 −5 E h or less), offering a practical route to highly accurate excited-state calculations with reduced computational overhead.

74 ATOMIC AND MOLECULAR PHYSICS↗

NASA NTRS1972

State of the art in the detection of intelligent extraterrestrial signals.

Recent progress in ideas of how signals that might represent electromagnetic radiations of intelligent civilizations elsewhere in the galaxy is summarized. Project Cyclops, carried out at Ames Research Center under the auspices of NASA and the American Society for Engineering Education, determined that microwaves are superior to lasers for interstellar signalling. It is felt that the band lying between the resonances of the two dissociation products of water, the hydrogen line at 1420 MHz, and the first hydroxyl line at 1662 MHz, is the most suitable. Phased antenna arrays of perhaps 1000 to 10,000 dishes of 100 m diam would be required. It is considered that a list of likely stars should be compiled, and these should be searched one at a time. Procedures for combing the spectrum are outlined.

Oliver, B. M.↗

NASA NTRS1993

Molecular processes in comets

A major effort was expended in developing procedures for calculating by quantum-mechanical methods the cross sections for the photodissociation of the hydroxyl radical OH. The molecule OH is the primary dissociation product of water and observations of OH when combined with a determination of the lifetime of OH in the solar radiation field can be used to calculate the rate of release of water from comets. There are many possible photodissociation channels whose efficiency depends upon the details of the spectrum of the radiation. We have calculated the potential energy curves of all the states of OH that can be reached by electric dipole absorption from the ground X(exp 2)(Pi) state by photons with energies up to about 12 eV.

Dalgarno, A.↗

NASA NTRS2015

Evolution of the Oxidation State of the Earth's Mantle

Danielson, L. R.↗

NASA NTRS2015

Evolution of the Oxidation State of the Earth's Mantle: Challenges of High Pressure Quenching

The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3+ at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. Experiments of more mafic compositions and at higher pressures commonly form a polyphase quench intergrowth composed primarily of pyroxenes, with interstitial glass which hosts nearly all of the more volatile minor elements. In our previous experiments on shergottite compositions, variable fO2, T, and P is less than 4 GPa, Fe3+/TotFe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3+/TotFe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3+. Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Experiments with Knippa basalt as the starting composition were conducted at 1-8 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products from 7-8 GPa quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal Fe3+/2+. A number of different approaches have been employed to produce glassy samples that can be measured by EELS and XANES. A more intermediate andesite was used in one experiment, and decompression during quenching was attempted after, but both resulted in a finer grained polyphase texture. Experiments are currently underway to test different capsule materials may affect quench texture. A preliminary experiment using liquid nitrogen to greatly enhance the rate of cooling of the assembly has also been attempted and this technique will be refined in further experiments.

Danielson, L. R.↗

DOE OSTI2023

Acid–Base Chemistry of a Model IrO 2 Catalytic Interface

Iridium oxide (IrO 2 ) is one of the most efficient catalytic materials for the oxygen evolution reaction (OER), yet the atomic scale structure of its aqueous interface is largely unknown. Herein, the hydration structure, proton transfer mechanisms and acid-base properties of the rutile IrO 2 (110)-water interface are investigated using ab-initio based deep neural-network potentials and enhanced sampling simulations. The proton affinities of the different surface sites are characterized by calculating their acid dissociation constants, which yield a point of zero-charge in good agreement with experiments. A large fraction (≈ 80%) of adsorbed water dissociation is observed, together with a short lifetime (≈ 0.5 ns) of the resulting terminal hydroxy groups, due to rapid proton exchanges between adsorbed H 2 O and adjacent OH species. As a result, this rapid surface proton transfer supports the suggestion that the rate-determining step in the OER may not involve proton transfer across the double layer into solution, as indicated by recent experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

An experimental study on gas-liquid phase fluid migration in hydrate-bearing sediments during hydrate dissociation

Natural gas hydrate production tests face problems such as severe sand blockage, poor gas-liquid phase separation, and significant land subsidence. This is because of the insufficient understanding of the complex phase transition and gas-liquid multi-phase fluid migration during hydrate dissociation. In hydrate-bearing sediment systems, hydrate phase transition couples with gas-liquid fluid migration. The phase transition causes changes in pore structure, which in turn modifies porous infiltration parameters and fluid flow capacity. Meanwhile, alterations in phase interfaces affect key parameters like surface tension and wettability. Gas-liquid fluid migration influences heat and mass transfer, thus affecting phase equilibrium and dissociation rates. To bridge the gap in describing gas-liquid fluid migration during hydrate dissociation in experiments, this research innovatively integrated an unsteady-state gas displacement by water and a quantitative hydrate dissociation process, independently developed a multi-phase seepage experimental system suitable for hydrate dissociation and determined the relationship between seepage parameters and hydrate saturation under different porosity. The results are as follows: a) Core samples with higher initial porosity show a greater recovery rate of fluid flow capacity. b) The retarding effect of multi-phase fluid has a more significant impact on the migration of the wetting phase fluid (water) than that of the non-wetting phase fluid (methane). c) During hydrate dissociation, the evolution of absolute permeability shows an “S-shaped” pattern, and the evolution of relative permeability shows a “wiring-harness” pattern. In conclusion, the findings can provide a theoretical basis for preventing geological disasters and for geotechnical engineering design during hydrate production.

58 GEOSCIENCES↗