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DOE OSTI2024

Electrochemical Control for Corrosion in Molten Chlorides During CSP Plant Operation

The Liquid Pathway of the Concentrating Solar Power Generation 3 (CSP Gen3) program proposed low-cost molten chloride salt for energy storage. However, online corrosion control was identified as a remining major risk of the Liquid Pathway approach. This project addressed that risk. Electrochemical solutions for corrosion mitigation during CSP plant operation were investigated and their feasibility and scalability were evaluated. The leading cause of corrosion in molten chloride salt systems was identified as corrosive impurities that form within the salt upon exposure to trace amounts of air and moisture. Leveraging electrochemistry, reduction/oxidation reactions can be employed to remove these corrosive impurities. In Phase 1 of this project, a bench-scale batch electrochemical reactor was designed, fabricated, and used to assess the kinetics and thermodynamics of electrochemical salt purification. In Phase 2, a laboratory-scale flow reactor was designed, fabricated, and used to assess the efficacy of the electrochemical method under flowing conditions. Results show that under proposed operating conditions for the Liquid Pathway Gen3 Pilot Plant, the electrochemical method is significantly more effective at removing impurities than alternative chemical and thermal methods, and that the electrochemical method produces less harmful byproducts. A key advance made in the course of this project was the development of a 2-electrode method for electrochemical purification that is more scalable than previously developed 3 electrode methods. This novel method is based on Magnesium (Mg) electrowinning. A provisional patent based on this invention has been submitted (USPTO Application No. 63/480,355). Additional key advances made during this project include assessment of the effect of dissimilar alloys on corrosion, kinetic and thermodynamic evaluation of thermolysis reactions of impurities within the molten salt, characterization of byproducts of purification reactions, and generation of IP focused on isolating value-added products using molten salt-based electrochemistry that could be deployed to valorize the process (USPTO Application No. 63/478,806). Ultimately, this project represented a step toward feasibility of Liquid Pathway Gen3 CSP. The method developed under this project could significantly reduce capital expenses and operating costs and increase plant profitability by enabling use of less expensive alloys, decreasing maintenance, and increasing plant longevity. Key focus areas for follow-on work have been identified as 1) evaluation of the efficacy of the electrochemical method under turbulent conditions in a larger flow system, such as the FASTR loop, 2) development of methods for removal of purification byproducts, 3) modeling pilot and industrial scale performance of electrochemical salt purification during plant operation and 4) further assessment of the effect of impurities on salt vapor phase.

14 SOLAR ENERGY↗

DOE OSTI2018

Spontaneous Reshaping and Splitting of AgCl Nanocrystals under Electron Beam Illumination

Abstract AgCl is photosensitive and thus often used as micromotors. However, the dynamics of individual AgCl nanoparticle motion in liquids upon illumination remains elusive. Here, using liquid cell transmission electron microscope (TEM), AgCl nanocrystals reshaping and splitting spontaneously in an aqueous solution under electron beam illumination are observed. It is found that the AgCl nanocrystals are negatively charged in the liquid environment, where the charge induces a repulsive Coulomb force that reshapes and stretches those nanocrystals. Upon extensive stretching, the AgCl nanocrystal splits into small nanocrystals and each nanocrystal retracts back into cuboid shapes due to the cohesive surface. This analysis shows that each nanocrystal maintains a single crystal rocksalt structure during splitting. The splitting of AgCl nanocrystals is analogous to the electrified liquid droplets or other reported the Coulomb fission phenomenon, but with distinctive structural properties. Revealing of the dynamic behavior of AgCl nanocrystals opens the opportunity to explore their potential applications as actuators for nanodevices.

Tian, Xuezeng↗

NASA NTRSDate not supplied

Development of thermostable carbonic anhydrases using structure-guided recombination for use in CO2 removal systems on spacecraft

Carbon capture and storage has been a research area of great interest in recent years asa method for mitigation of CO2emissions, due to the effects of climate change. The development of technologies for the efficient capture of CO2are also of great interest for human spaceflight applications. One of the most promising technologies in this area is CO2 scrubbing using liquid amines, unfortunately, liquid amines with low heats of desorption tend to have slow CO2binding kinetics. One potential solution to this problem is to use the enzyme carbonic anhydrase (CA) to enhance the kinetics of CO2binding to liquid amines, allowing the overall process to be more energy efficient. Interest in using carbonic anhydrase as a biocatalyst has led to a number of efforts to improve the thermostability and solvent tolerance of several distinct carbonic anhydrase enzymes. In the work described here, we screened through a diverse set of natural carbonic anhydrases to identify candidates for protein engineering aimed at increased stability and activity in various liquid amines. We then used SCHEMA structure-guided recombination to develop a set of chimeric carbonic anhydrases with high thermostability and activity. These chimeras were used as the starting points for further protein engineering work targeting activity in liquid amine systems. Our ultimate goal is to test the engineered enzymes in a liquid amine system for cabin air revitalization on ISS or other spacecraft.

Life Support↗

DOE OSTI2021

Crowded electrolytes containing redoxmers in different states of charge: Solution structure, properties, and fundamental limits on energy density

Nonaqueous redox flow batteries use liquid electrolytes containing redox-active organic molecules (redoxmers) as their energy storage medium. To maximize energy density, the redoxmer concentration needs to be maximized while maintaining low viscosity and high ionic conductivity. During charge, a redoxmer molecule pairs with an ion in the electrolyte while another ion migrates across the membrane to maintain electric neutrality. In a crowded electrolyte, this reconstitution changes physical and chemical properties of the solution. To explore these behaviors, a phenothiazine redoxmer fully miscible with acetonitrile was used, and electrochemical charge was mimicked by chemical oxidation. The solutions were examined using small-angle X-ray scattering, nuclear magnetic resonance, and conductometry and modeled using classical molecular dynamics. Overall, our study indicates that physical and structural properties of redoxmer solutions in both states of charge make it exceedingly difficult to increase the redoxmer concentrations over 2 M at any temperature without compromising dynamic properties of such solutions. The cause for this limitation is proximity to a gel-like regime in which fluidity, diffusivity, and ionic conductivity exponentially decrease with increasing concentration. This tendency is compounded by non-Arrhenius behavior of the electrolyte: a small increase in the concentration outruns gains in fluidity and conductivity at a higher temperature. Thus the properties of crowded electrolytes generally make it impossible to operate when gel-like behavior sets in. Pushing the redoxmer concentration to 2.5-3 M might be possible for small redoxmer molecules, but it would require the use of ionic liquid electrolytes at 340-360 K. (C) 2021 Elsevier B.V. All rights reserved.

25 ENERGY STORAGE↗

NASA NTRS1999

The Heterogeneous Chemistry of Acetone in Sulfuric Acid Solutions: Implications for the Upper Troposphere

The uptake of acetone vapor by liquid sulfuric acid has been investigated over the range of 40-87 wt. %H(sub 2)SO(sub 4) and between the temperatures 198 to 300K.

Heterogenous Chemistry Acetone Sulfuric Acid↗

DOE OSTI2015

Do protein crystals nucleate within dense liquid clusters?

The evolution of protein-rich clusters and nucleating crystals were characterized by dynamic light scattering (DLS), confocal depolarized dynamic light scattering (cDDLS) and depolarized oblique illumination dark-field microscopy. Newly nucleated crystals within protein-rich clusters were detected directly. These observations indicate that the protein-rich clusters are locations for crystal nucleation. Protein-dense liquid clusters are regions of high protein concentration that have been observed in solutions of several proteins. The typical cluster size varies from several tens to several hundreds of nanometres and their volume fraction remains below 10{sup −3} of the solution. According to the two-step mechanism of nucleation, the protein-rich clusters serve as locations for and precursors to the nucleation of protein crystals. While the two-step mechanism explained several unusual features of protein crystal nucleation kinetics, a direct observation of its validity for protein crystals has been lacking. Here, two independent observations of crystal nucleation with the proteins lysozyme and glucose isomerase are discussed. Firstly, the evolutions of the protein-rich clusters and nucleating crystals were characterized simultaneously by dynamic light scattering (DLS) and confocal depolarized dynamic light scattering (cDDLS), respectively. It is demonstrated that protein crystals appear following a significant delay after cluster formation. The cDDLS correlation functions follow a Gaussian decay, indicative of nondiffusive motion. A possible explanation is that the crystals are contained inside large clusters and are driven by the elasticity of the cluster surface. Secondly, depolarized oblique illumination dark-field microscopy reveals the evolution from liquid clusters without crystals to newly nucleated crystals contained in the clusters to grown crystals freely diffusing in the solution. Collectively, the observations indicate that the protein-rich clusters in lysozyme and glucose isomerase solutions are locations for crystal nucleation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2019

Understanding Nitrate Chemistry - The Key to Safer and More Efficient TRU Waste Acceptance - 19618

Investigations into the Waste Isolation Pilot Plant (WIPP) radiological release from a transuranic (TRU) waste drum concluded that the event was initiated by a thermal runaway, principally involving interactions between the polysaccharide-based kitty litter and nitric acid, which released radiological material along with hot gases and combustible materials from the drum. In this paper, the hazards of polysaccharides present as either starch based kitty litter or cellulose rags in a TRU waste drum exposed to nitric acid (and by extension metal nitrate salts) have been evaluated, based on considerations of how complex nitrogen redox cycles carry out the aqueous phase oxidation of alcohols and related organic functional groups. These exothermic reactions, coupled with a positive feedback loop inherent to nitrogen redox chemistry, can initiate an autocatalytic thermal runaway and explosive gas generation, which poses the most significant risk under ambient conditions where acidic solution may be present (in small quantities as free liquid or sorbed within a solid matrix). Nitric acid is an extremely potent oxidant but is itself remarkably inert, rarely interacting directly with oxidizable substrates and instead exerting its vast potential energy through lower oxidation state reactants such as nitrogen dioxide and nitrous acid that are generated from its slow self-decomposition. Nitrous acid is the reactant that carries out substrate oxidation, and systems that are not pre-loaded with nitrous acid will experience an induction period before significant reactivity commences. Under oxidizing fuel-lean conditions, nitrogen dioxide may induce autocatalytic nitrous acid formation, which may supplement additional side-reactions, potentially leading to thermal runaway. Therefore, the system is most vulnerable at the end of an induction period. Metal nitrate salts promote this ambient temperature solution chemistry (cf. traditional oxidizer properties of metal nitrate salts, which operate in the solid state at elevated temperatures) by releasing nitric acid into the system via hydrolysis. Unlike simple alcohols with a single hydroxyl functional group, the chemistry of polymeric carbohydrates (polysaccharides) such as starches and cellulose is more diverse. Therefore, the oxidation of the simple monomeric carbohydrate glucose is first examined to provide insight into the analogous reactivity with polysaccharides. Although less reactive than alcohols by virtue of extensive hydrogen bonding, carbohydrates are oxidized by nitric acid through the same fundamental mechanisms, complicated by a variety of competing side reactions including acid-catalyzed hydrolytic depolymerization to more reactive (ultimately monomeric) units, as well as other degradation reactions promoted by radical mechanisms. For this reason, polysaccharides such as starches that are more susceptible to hydrolysis are more reactive than cellulose, with the attendant microbial population in starch based kitty litter adding a special aspect of reactivity. From this safety evaluation, a bounding latency period has been developed beyond which a stored TRU waste drum that contains polysaccharides (starch based kitty litter excluded) commingled with nitric acid and/or metal nitrate salts may no longer present a hazard under ambient conditions, based on a compilation of induction periods and reaction times involving nitric acid with various oxidizable substrates under a variety of conditions from synthetic procedures, tests, and adverse incident scenarios. By obviating the need for costly treatment options or characterization, a better understanding of nitrate redox chemistry and the hazards it presents with polysaccharide oxidation thus provides a more efficient means to safely dispose of TRU waste generated within the Department of Energy (DOE) complex. (author)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS1993

Development and verification of methods for predicting flow rates through leaks in valves and couplings

This is the final report of a research effort which addresses the title problem. The report discusses two broad models of flows, which represent the following extreme cases: (1) inertia-dominated flow, where friction is relatively insignificant; and (2) friction-dominated flow where inertia is insignificant. In class (2), the leak channel might consist of the gap between a scratch in a plastic seal and a polished metal plate against which the seal is pressed. Here, the cross section of the leak channel is modeled as a flat bottomed crescent. A publication generated under the present grant period presents an exact solution of the equations of fully-developed laminar pipe flow of a liquid in the case of a crescent beneath a hyperbolic arc. A Master's thesis project supported by the present grant presents the corresponding solution beneath a circular arc. A second publication reviews the flow of a gas through the same channel, which may be analyzed by a standard one-dimensional model (Fanno flow) for an engineering approximation. Finally, the report discusses the design and progress in the fabrication of a leak-test cell, in which one may measure the flow of fluid through a controlled flaw in a seal. The aim of such measurements is to furnish data for comparison with the predictions of the theory.

Russell, John M.↗

DOE OSTI2022

The Use of Acoustic Cavitation to Recovery High-Assay Low-Enriched Uranium (HALEU) form TRISO Fuel Particles

Recent interest in advanced nuclear reactor concepts such as small modular reactor (SMR), micro reactor or versatile test reactor (VTR) has increased the demand for high-assay, low-enriched uranium (HALEU). The sustainable management of this resource is integral to successful resurgence of nuclear energy in the United States. The High Temperature Gas-Cooled Reactor (HTGR) concept is a prime candidate for deployment of the new fleet of SMRs, and it will become very important to have a simple and cost-effective technology to recover HALEU from short-burned, defective, or off-specification TRISO fuel particles. We have attempted to harness the high energetics of sonochemistry to penetrate the TRISO fuel particles and recover HALEU via acidic leaching. While the TRISO fuel particle design is inherently “bulletproof,” (due to the silicon carbide (SiC) layer), ultrasonic irradiation may hold the key to convenient access to its valuable contents. Sonochemistry is a field of chemistry based on acoustic cavitation, which is the formation, growth, and collapse of bubbles in liquid media.1,2 The oscillating bubble formation is produced by irradiation of a liquid media with sound waves. Literature reports indicate that collapsing bubbles induced by cavitation produces intense local heating, high pressures, and short lifetimes.1 These localized hot spots reach temperatures of ˜5000 K, pressures approaching 500 atm, and heating and cooling rates exceeding 100 K/s.1 The large temperature and pressure differentials deliver high-energy heating and microscopic explosive shock waves to a liquid media or liquid/solid interface. Cavitation at the surface of a solid in solution induces a deformation in the bubble cavity upon collapse. This deformation reinforces the bubble structure and sends a fast-moving stream of liquid through the cavity at the surface with velocities greater than 100 m/s.3 These energetic impacts have demonstrated an ability to penetrate or simply destroy the SiC shell surrounding the uranium fuel kernel during prolonged exposures to the high-power acoustic waves. Some preliminary results demonstrating HALEU recovery using sonochemistry techniques will be reported.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2013

Systems and methods for laser assisted sample transfer to solution for chemical analysis

Systems and methods are described for laser ablation of an analyte from a specimen and capturing of the analyte in a dispensed solvent to form a testing solution. A solvent dispensing and extraction system can form a liquid microjunction with the specimen. The solvent dispensing and extraction system can include a surface sampling probe. The laser beam can be directed through the surface sampling probe. The surface sampling probe can also serve as an atomic force microscopy probe. The surface sampling probe can form a seal with the specimen. The testing solution including the analyte can then be analyzed using an analytical instrument or undergo further processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

Systems and methods for laser assisted sample transfer to solution for chemical analysis

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Systems and methods for laser assisted sample transfer to solution for chemical analysis

47 OTHER INSTRUMENTATION↗

DOE OSTI2024

Development of Modified Perturbation Solutions to the One-Phase Stefan Problems With a Convective Boundary

The classical Stefan problem is used to track the moving solid-liquid interface during the freezing process. Perturbation theory has often been applied to find an approximate analytical solution due to the nonlinearity of the moving interface. However, the Stefan number (i.e., the sensible over latent heat) must be small and usually less than 0.01 to assume the perturbation expansion, which in turn limits the thermal engineering applications. In this study, a modified perturbation solution is developed by adding a correction term after the leading-order solution to be valid for a much wider range of Stefan numbers (i.e., 0.01 less than or equal to Ste less than or equal to 1). Specifically, a one-phase Stefan problem is first formulated subjected to a convective boundary in the Cartesian, cylindrical, and spherical coordinate systems for inward solidification. The leading-order solution is calculated based on the regular perturbation theory, while the correction term is obtained using the Monte-Carlo method and a multi-variant regression. Results show that the correction term has a linear relationship with the Stefan number and is not significantly influenced by the Biot number. The proposed modified perturbation solution can accurately and rapidly predict the nonlinear moving interface motion for the freezing process.

DIRECT ENERGY CONVERSION,MATHEMATICS AND COMPUTING↗

DOE OSTI2013

NOCHAR Polymers: An Aqueous and Organic Liquid Solidification Process for Cadarache LOR (Liquides Organiques Radioactifs) - 13195

To handle the Very Low Level Waste (VLLW) and the Low Level Waste (LLW) in France, two options can be considered: the incineration at CENTRACO facility and the disposal facility on ANDRA sites. The waste acceptance in these radwaste routes is dependent upon the adequacy between the waste characteristics (physical chemistry and radiological) and the radwaste route specifications. If the waste characteristics are incompatible with the radwaste route specifications (presence of significant quantities of chlorine, fluorine, organic component etc or/and high activity limits), it is necessary to find an alternative solution that consists of a waste pre-treatment process. In the context of the problematic Cadarache LOR (Liquides Organiques Radioactifs) waste streams, two radioactive scintillation cocktails have to be treated. The first one is composed of organic liquids at 13.1 % (diphenyloxazol, mesitylene, TBP, xylene) and water at 86.9 %. The second one is composed of TBP at 8.6 % and water at 91.4 %. They contain chlorine, fluorine and sulphate and have got alpha/beta/gamma spectra with mass activities equal to some kBq.g{sup -1}. Therefore, tritium is present and creates the second problematic waste stream. As a consequence, in order for disposal acceptance at the ANDRA site, it is necessary to pre-treat the waste. The NOCHAR polymers as an aqueous and organic liquid solidification process seem to be an adequate solution. Indeed, these polymers constitute an important variety of products applied to the treatment of radioactive aqueous and organic liquids (solvent, oil, solvent/oil mixing etc) and sludge through a mechanical and chemical solidification process. For Cadarache LOR, N910 and N960 respectively dedicated to the organic and aqueous liquids solidification are considered. With the N910, the organic waste solidification occurs in two steps. As the organic liquid travels moves through the polymer strands, the strands swell and immobilise the liquid. Then as the polymer-organic cure, over time, the polymer continues to collapse on the organic to create a permanent bond. The N960 has the ability to absorb aqueous waste up to 100 times its own weight. It creates a strong mechanical bond which permanently traps the contamination imbedded in the aqueous liquids. As a consequence, these two polymers seem to be able to constitute a suitable solidification matrix for a final acceptance in storage on ANDRA sites. In order to validate the polymers as an acceptable aqueous and organic solidification process for Cadarache LOR, some solidification tests realized with N910 and N960, have been carried out for different Waste/Polymer ratios. The determination of the best Waste/Polymer ratio and of the optimal experimental parameters has been made through an exudation test. Indeed, the process prevents leaching and it results in the absence of residual free organic or aqueous liquid which is forbidden in storage by ANDRA specifications. With these test results, we generated scientific data which are fundamental to obtain an ANDRA agreement. As a conclusion, the aim of this study is to demonstrate that the solidification by polymers can constitute a pre-treatment solution for Cadarache LOR and more generally, for various organic and mixed organic/aqueous waste which can not be directly acceptable at CENTRACO facility or at ANDRA storage sites. This work is, therefore, a solid background to demonstrate the feasibility of the waste pre-treatment by solidification with polymers and to encourage the development of this process. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2022

DFT-based QM/MM with Particle-Mesh Ewald for Direct, Long-Range Electrostatic Embedding

In this work, we present a DFT-based, QM/MM implementation with long-range electrostatic embedding achieved by direct real-space integration of the particle mesh Ewald (PME) computed electrostatic potential. The key transformation is the interpolation of the electrostatic potential from the PME grid to the DFT quadrature grid, from which integrals are easily evaluated utilizing standard DFT machinery. We provide benchmarks of the numerical accuracy with choice of grid size and real-space corrections, and demonstrate that good convergence is achieved while introducing nominal computational overhead. Furthermore, the approach requires only small modification to existing software packages, as is demonstrated with our implementation in the OpenMM and Psi 4 software. After presenting convergence benchmarks, we evaluate the importance of long-range electrostatic embedding in three solute/solvent systems modeled with QM/MM. Water and BMIM/BF 4 ionic liquid were considered as "simple" and "complex" solvents respectively, with water and p-phenylenediamine (PPD) solute molecules treated at QM level of theory. While electrostatic embedding with standard real-space truncation may introduce negligible error for simple systems such as water solute in water solvent, errors become more significant when QM/MM is applied to complex solvents such as ionic liquids. An extreme example is the electrostatic embedding energy for oxidized PPD in BMIM/BF 4 for which real-space truncation produces severe error even at 2-3 nm cutoff distances. This latter example illustrates that utilization of QM/MM to compute redox potentials within concentrated electrolytes/ionic media requires carefully chosen long-range electrostatic embedding algorithms, with our presented algorithm providing a general and robust approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Iron(III) Speciation Observed at Aqueous and Glycerol Surfaces: Vibrational Sum Frequency and X-ray

Aqueous solutions of FeCl 3 have been widely studied to shed light on a number of processes from dissolution, mineralization, biology, electrocatalysis, corrosion, to microbial biomineralization. Yet there are little to no molecular level studies of the air–liquid FeCl 3 interface. Here, both aqueous and glycerol FeCl 3 solution surfaces are investigated with polarized vibrational sum frequency generation (SFG) spectroscopy. We also present the first ever extreme ultraviolet reflection–absorption (XUV-RA) spectroscopy measurements of solvated ions and complexes at a solution interface, and observe with both X-ray photoelectron spectroscopy (XPS) and XUV-RA the existence of Fe(III) at the surface and in the near surface regions of glycerol FeCl 3 solutions, where glycerol is used as a high vacuum compatible proxy for water. XPS showed Cl - and Fe(III) species with significant Fe(III) interfacial enrichment. In aqueous solutions, an electrical double layer (EDL) of Cl - and Fe(III) species at 0.5 m FeCl 3 concentration is observed as evidenced from an enhancement of molecular ordering of water dipoles, consistent with the observed behavior at the glycerol surface. At higher concentrations in water, the EDL appears to be substantially repressed, indicative of further Fe(III) complex enrichment and dominance of a centrosymmetric Fe(III) species that is surface active. In addition, a significant vibrational red-shift of the dangling OH from the water molecules that straddle the air–water interface reveals that the second solvation shell of the surface active Fe(III) complex permeates the topmost layer of the aqueous interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1994

Determination of a transient heat transfer property of acrylic using thermochromic liquid crystals

An experiment was performed to determine a transient heat transfer property of acrylic. The experiment took advantage of the known analytical solution for heat conduction in a homogeneous semi-infinite solid with a constant surface heat flux. Thermochromic liquid crystals were used to measure the temperature nonintrusively. The relevant property in this experiment was the transient thermal conduction coefficient h(sub t), which is the square root of the product of density p, specific heat c(sub p), and thermal conductivity k (i.e., square root of pc(sub p)k). A value of 595.6 W square root of s/sq m K was obtained for h(sub t), with a standard deviation of 5.1 W square root of s/sq m K. Although there is no generally accepted value for h(sub t), a commonly used one is 580 W square root of s/sq m K, which is almost 3 percent less than the h(sub t) value obtained in this experiment. Since these results were highly repeatable and since there is no definitive value for h(sub t), the new value is recommended for future use.

Heidmann, James D.↗

DOE OSTI2015

A hybrid framework of first principles molecular orbital calculations and a three-dimensional integral equation theory for molecular liquids: Multi-center molecular Ornstein–Zernike self-consistent field approach

In this study, we reported the development of a new quantum mechanics/molecular mechanics (QM/MM)-type framework to describe chemical processes in solution by combining standard molecular-orbital calculations with a three-dimensional formalism of integral equation theory for molecular liquids (multi-center molecular Ornstein–Zernike (MC-MOZ) method). The theoretical procedure is very similar to the 3D-reference interaction site model self-consistent field (RISM-SCF) approach. Since the MC-MOZ method is highly parallelized for computation, the present approach has the potential to be one of the most efficient procedures to treat chemical processes in solution. Benchmark tests to check the validity of this approach were performed for two solute (solute water and formaldehyde) systems and a simple S{sub N}2 reaction (Cl{sup −} + CH{sub 3}Cl → ClCH{sub 3} + Cl{sup −}) in aqueous solution. The results for solute molecular properties and solvation structures obtained by the present approach were in reasonable agreement with those obtained by other hybrid frameworks and experiments. In particular, the results of the proposed approach are in excellent agreements with those of 3D-RISM-SCF.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗