Predicting the pair correlation functions of silicate and borosilicate glasses using machine learning.

Glasses offer a broad range of tunable thermophysical properties that are linked to their compositions. However, it is challenging to establish a universal composition-property relationship of glasses due to their enormous compositions and chemical space. Here, we address this problem and develop a metamodel of the composition-atomistic structure relationship of a class of glassy materials via a machine learning (ML) approach. Within this ML framework, an unsupervised deep learning technique, viz., a convolutional neural network (CNN) autoencoder, and a regression algorithm, viz. random forest (RF), are integrated into a fully automated pipeline to predict the spatial distribution of atoms in a glass. The RF regression model predicts the pair correlation function of a glass in a latent space. Subsequently, the decoder of the CNN converts the latent space representation to the actual pair correlation function of the given glass. The atomistic structures of silicate (SiO2) and sodium borosilicate (NBS) based glasses with varying compositions and dopants are collected from molecular dynamics (MD) simulations to establish and validate this ML pipeline. The model is found to predict the atom pair correlation functions for many unknown glasses very accurately. This method is very generic and can accelerate the design, discovery, and fundamental understanding of the composition-atomistic structure relationship of glasses and other materials.

Efficient Removal of Uranyl Ions Using PAMAM Dendrimer: Simulation and Experiment.

In this work, using atomistic molecular dynamics (MD) simulations and polymer-assisted ultrafiltration experiments, we explore the adsorption and removal of uranyl ions from aqueous solutions using poly(amidoamine) (PAMAM) dendrimers. The effects of uranyl ion concentration and the pH of the solution were examined for PAMAM dendrimers of generations 3, 4, and 5. Our simulation results show that PAMAM has a high adsorption capacity for the uranyl ions. The adsorption capacity increases with increasing concentration of uranyl ions for all 3 generations of PAMAM in agreement with experimental findings. We find that the number of uranyl ions bound to PAMAM is significantly higher in acidic solutions (pH < 3) as compared to neutral solutions (pH ∼ 7) for all uranyl ion concentrations. Additionally, we find an increase in the number of adsorbed uranyl ions to PAMAM with the increase in the dendrimer generation. This increase is due to the greater number of binding sites present for higher-generation PAMAM dendrimers. Our simulation study shows that nitrate ions form a solvation shell around uranyl ions, which allows them to bind to PAMAM binding sites, including the amide, amine, and carbonyl groups. In polymer-assisted ultrafiltration (PAUF) experiments, the removal percentage of uranyl ions by G3 PAMAM dendrimer increased from 36.3% to 42.6% as the metal ion concentration increased from 2.1 × 10-5 M to 10.5 × 10-5 M at a pH of 2. Our combined experiment and simulation study suggests that PAMAM is an effective adsorbent for removing uranyl ions from aqueous solutions.

Simple, Fast, and Selective Dissolution of Eu2O3 in an Ionic Liquid as a Sustainable Paradigm for Lanthanide-Actinide Separations in Radioactive Waste Remediation.

The liquid-liquid extraction (LLE) process for lanthanide-actinide separation from the nuclear fuel cycle has several drawbacks such as, the requirement of cooling for decay heat control, the handling of large volumes of toxic volatile organic compounds (VOCs), and secondary waste generation. Alternatively reprocessing without spent fuel cooling is done by pyroprocessing, which uses high-temperature corrosive molten salts and requires elevated temperature, and is an energy-intensive process. In recent years, some of the shortcomings of both LLE and pyroprocessing are overcome by the use of room temperature ionic liquids (RTILs) as the solvents. In the present work, an attempt was made to exploit the potential of the neoteric, less-corrosive, low-VOC RTILs toward direct dissolution-based separations at ambient conditions. The present paper involves the selective dissolution of Eu2O3 in an RTIL, i.e., C4mim·NTf2 containing 2-thenoyltrifluoroacetone (HTTA) within ca. 30 min at ambient conditions; while the dissolution of AmO2 and UO2 were found to be very poor, making this an attractive method for lanthanide-actinide separation, a key step in radioactive waste management, i.e., an actinide partitioning and transmutation strategy. The quantitative dissolution of Eu2O3 from simulated spent nuclear fuel with different Eu2O3 loading was also shown. Water plays a crucial role in deciding the kinetics of dissolution and amount of the dissolved oxide. The combination of X-ray absorption, fluorescence, and UV-vis spectroscopic studies suggested the formation of the dehydrated anionic complex Ln(TTA)4- to play pivotal role in the oxide dissolution process. The structure of the complex was analyzed by density functional theory and extended X-ray absorption fine structure. The mechanism of oxide dissolution was proposed and electrochemical studies were performed to understand the possible recovery option using electrodeposition of the dissolved Eu3+.

Structure and dynamics of the Li+ ion in water, methanol and acetonitrile solvents: ab initio molecular dynamics simulations.

Fundamental understanding of the structure and dynamics of the Li+ ion in solution is of utmost importance in different fields of science and technology, especially in the field of ion batteries. In view of this, ab initio molecular dynamics (AIMD) simulations of the LiCl salt in water, methanol and acetonitrile were performed to elucidate structural parameters such as radial distribution function and coordination number, and dynamical properties like diffusion coefficient, limiting ion conductivity and hydrogen bond correlation function. In the present AIMD simulation, one LiCl in water is equivalent to 0.8 M, which is close to the concentration of the lithium salt used in the Li-ion battery. The first sphere of coordination number of the Li+ ion was reaffirmed to be 4. The radial distribution function for different pairs of atoms is seen to be in good agreement with the experimental results. The calculated potential of mean force indicates the stronger interaction of the Li+ ion with methanol over water followed by acetonitrile. The dynamical parameters convey quite high diffusion and limiting ionic conductivity of the Li+ ion in acetonitrile compared to that in water and methanol which has been attributed to the transport of the Li-Cl ion pair in a non-dissociated form in acetonitrile. The AIMD results were found to be in accordance with the experimental findings, i.e. the limiting ion conductivity was found to follow the order acetonitrile > methanol > water. This study shows the importance of atomistic level simulations in evaluating the structural and dynamical parameters and in implementing the results for predicting and synthesizing better next generation solvents for lithium ion batteries (LIBs).

Unexplored Isomerization Pathways of Azobis(benzo-15-crown-5): Computational Studies on a Butterfly Crown Ether.

Computational studies on trans → cis and cis → trans isomerizations of photoresponsive azobis(benzo-15-crown-5) have been reported in this work. The photoexcited ππ* state (S2) of the trans isomer relaxes through the planar S2 minimum and the planar S2/S1 conical intersection (both situated around 9 kcal/mol below the vertically excited S2 state) arising along the N═N stretching coordinate. The nπ* state (S1) of this isomer has both planar and rotated (clockwise and anticlockwise) minima, which may lead to a torsional conical intersection (S0/S1) geometry having a

Tuning Network Connectivity of Silicate and Sodium Borosilicate Glasses by TiO2 for Enhanced Chemical Durability: Molecular Dynamics Simulation Investigations.

Extensive molecular dynamics (MD) simulations were performed to disclose the beneficial aspects of TiO2 doping in SiO2 and sodium borosilicate (NBS) glasses. Significant amendment in short- and intermediate-range orders of glasses was captured by the radial distribution function, coordination number, bond/angle distribution profiles, structure factor, and probability of linking X-O-X' (where X and/or X' = Si, B, and Ti) structural motifs. Successively, the effect of microscopic structural modification on the macroscopic properties was analyzed in terms of mechanical strength, thermal stability, vibrational characteristics [(vibrational density of states (VDOS)], and chemical durability. The results show that Ti participates in the network chain in the form of TiO6 and TiO5 for the Ti-NBS glass whereas in the form of TiO6, TiO5, and TiO4 for the binary TiO2-SiO2 glass. The presence of TiO2 was found to strengthen the glass skeleton. However, the glass-transition temperature was also increased with Ti addition, which indicates increased hurdles during synthesis due to increased cross connections in the glass network with Ti doping. The computed results envisage enhanced chemical durability of Ti-added glasses. In addition, VDOS spectra showed network former-like characteristics of Ti in the glass network with significant contributions up to a vibration frequency of 800 cm-1. The strong binding of Ti-O-connected Na+ in the glass skeleton prevents Na+ migration toward the interface or bulk aqueous phase, which contributes to improved chemical stability of Ti-containing glasses. During contact with water, Na+ were less likely to leach out from glass to the aqueous solution during Ti doping. In addition, the increased fraction of stable ring structures (5m-7m) for Ti-NBS glasses than bare NBS glasses also supports the increased leaching resistivity of Ti-added glasses. Essentially, the elucidation of macroscopic glass properties has been provided in terms of microscopic understanding. The present findings will incite further MD simulations and experiments to disclose more interesting microstructures and dynamics due to the presence of TiO2 in glasses.

Aggregation Behavior of Nitrilotriacetamide (NTAmide) Ligands in Thorium(IV) Extraction from Acidic Medium: Small-Angle Neutron Scattering, Fourier Transform Infrared, and Theoretical Studies.

Two tripodal amides obtained from nitrilotriacetic acid with n-butyl and n-octyl alkyl chains (HBNTA(LI) and HONTA(LII), respectively) were studied for the extraction of Th(IV) ions from nitric acid medium. The effect of the diluent medium, i.e., n-dodecane alone and a mixture of n-dodecane and 1-decanol, onto aggregate formation were investigated using small angle neutron scattering (SANS) studies. In addition, the influence of the ligand structure, nitric acid, and Th(IV) loading onto ligand aggregation and third-phase formation tendency was discussed.The LI/LII exist as monomers (aggregarte radius for LI: 6.0 Å; LII:7.4 Å) in the presence of 1-decanol, whereas LII forms dimers (aggregarte radius for LII:9.3 Å; LI does not dissolve in n-dodecane) in the absence of 1-decanol. The aggregation number increases for both the ligands after HNO3 and Th(IV) loading. The maximum organic concentration (0.050 ± 0.004 M) of Th(IV) was reached without third-phase formation for 0.1 M LI/LII dissolved in 20% isodecanol +80% n-dodecane. The interaction of 1-decanol with LII and HNO3/Th(IV) with amidic oxygens of LI/LII results in shift of carbonyl stretching frequency, as shown by attenuated total reflectance-Fourier transform infrared (ATR-FTIR) studies. The structural and bonding information of the Th-LI/LII complex were derived from the density functional theoretical (DFT) studies. The molecular dynamics (MD) simulations suggested that the aggregation behavior of the ligand in the present system is governed by the population of hydrogen bonds by phase modifier around the ligand molecules. Although the theoretical studies suggested higher Gibbs free energy of complexation for Th4+ ions with LI than LII, the extraction was found to be higher with the latter, possibly due to the higher lipophilicity and solubility of the Th-LII aggregate in the nonpolar media.

An insight into the sequestration of tetra and hexavalent actinides by tri ethoxysilyl-amino-propyl-3-oxa-glutaramic acid (SAPOGA) functionalized titania.

Silyl-amino-propyl-3-oxa-glutaramic acid (SAPOGA) functionalized titania has been synthesized for highly efficient solid phase sequestration of thorium and uranyl ions from an aqueous acidic waste stream. The XRD pattern suggested that the grafting was performed on the anatase phase, leading to a rougher surface resulting in better interaction with actinides. The successful grafting of SAPOGA bridging was confirmed using spectroscopic methods. The Langmuir isotherm and the intraparticle diffusion-based kinetics model were found to be operative with sorption capacities of 231 mg g-1 and 458 mg g-1 and rate constants of 51 mg g-1 min-1 and 48 mg g-1 min-1 for U and Th, respectively. The entropy driven sequestration process was thermodynamically favourable (ΔGU = -6.0 kJ mol-1 and ΔGTh = -9.1 kJ mol-1) and endothermic in nature. The experimentally corroborated complexation pattern was assisted by density functional theory (DFT) calculations, which gave further insight into the metal-ligand interaction.

In Situ Preconcentration during the Di-(2-ethylhexyl) Phosphoric Acid-Assisted Dissolution of Uranium Trioxide in an Ionic Liquid: Spectroscopic, Electrochemical, and Theoretical Studies.

Dissolution of uranium oxide was carried out using a solution of HD2EHP in C8mim·NTf2, which was apparently facilitated by the in situ generation of water during the complex formation reaction. The dissolved complex in the ionic liquid phase led to splitting of the latter into a light phase and a heavy phase where the former contained predominantly the UO2(HL2)2 complex (HL = HD2EHP), while the latter contained the ionic liquid as supported by FTIR and UV-Visible spectral analyses. The complexation of the uranyl ion was suggested to take place in the equatorial plane where two dimeric units of the H-bonded HD2EHP molecules took part in complexation. An increase in temperature facilitated the dissolution rate with an activation energy of 31.0 ± 2.8 kJ/mol. The cyclic voltammetry studies indicated potential chances of recovery of the dissolved uranium by electrodeposition at the cathode. The proposed dimeric structure of HD2EHP in the complexation with U(VI) was supported by DFT studies also.

Molecular dynamics simulations of simplified sodium borosilicate glasses: the effect of composition on structure and dynamics.

The fusion of valuable material properties has led to the acceptance of sodium borosilicate (NBS) glasses for nuclear waste immobilization. Although popular, the mechanisms associated with these properties are still only partially discovered and need further exploration. Bearing this in mind, the combination of experiments, molecular dynamics (MD) simulations and the Dell, Yuan and Bray model have been used to understand the role of composition variation for structural and physical aspects of vitrified borosilicate glasses. Experiments have been conducted to evaluate the macroscopic glass parameters of density (ρ), glass transition temperature (Tg) and thermal expansion coefficient (TEC). Experimentally observed trends for ρ, Tg and TEC with composition have been found in good agreement with the MD results. MD studies also provide a microscopic understanding of the glass structure and phenomena associated with the change in the glass composition. A detailed view of local structure and medium-range connectivity for the borosilicate glasses has been explored. Owing to a large B4 population, the results showed the abundant presence of BO4-BO4 connections, we hereby omit the generally accepted "B[4] avoidance rule" for glass. The relative propensity for connecting SiO4/BO3/BO4 structural motifs is in line with the predictions made by the Dell, Yuan and Bray model. Furthermore, the effects of composition on the mechanical integrity of NBS glasses, including the elastic nature, plastic distortion, yielding, breaking stress, and brittle fracture, have been explored by MD simulations. In addition, the glass dynamics have been evaluated by diffusion coefficient and the results suggest that Na+ is likely to be more mobile in the case of NBS1 as compared to NBS2 and NBS3 due to significant disruption in the glass network introduced by a larger amount of Na2O network modifier. Also, the diffusivity was reduced with increasing B2O3 due to the altered role of Na+ ions from network modifiers to charge compensators. The combined study of experiments, MD simulations and the Dell, Yuan and Bray model establish the correlation between the microscopic structure and macroscopic properties of NBS glasses with varied composition, which might be of great scientific use for future glasses in various applications including nuclear waste immobilization.

Highly Efficient N-Pivot Tripodal Diglycolamide Ligands for Trivalent f-Cations: Synthesis, Extraction, Spectroscopy, and Density Functional Theory Studies.

A series of four N-pivot tripodal diglycolamide (DGA) ligands, where three DGA moieties are attached to the central N atom via spacers of different lengths and with varying alkyl substituents on the amidic nitrogen of DGA (LI-LIV), were studied for their extraction and complexation ability toward trivalent lanthanide/actinide ions, including solvent extraction, complexation using spectrophotometric titrations, and luminescence spectroscopic studies. Introduction of a methyl group on the amidic nitrogen atom gives rise to a 400 fold increase of the Eu distribution ( D) value [LIII (NMe) vs LII (NH)] at 1 M HNO3. Enlargement of the spacer length between the pivotal N atom and the DGA moieties with one carbon atom results in a 14 times higher DEu value [LI (C3) vs LII (C2)]. Slope analyses showed that Eu3+ was extracted as a bis-solvated species with all four ligands. The compositions of the Eu3+/L complexes were further confirmed by spectroscopic measurements, its formation constants following the order: LIII > LIV > LI > LII. Luminescence spectroscopy and electrospray ionization mass spectrometry revealed that all four ligands form [Eu(L)2(NO3)3] complexes. Density functional theory and thermodynamic parameters corroborated the existence of [Eu(L)2(NO3)3] complexes.

Reduction in Coordination Number of Eu(III) on Complexation with Pyrazine Mono- and Di-Carboxylates in Aqueous Medium.

The denticity, flexibility, and steric hindrance of the ligand are key factors in deciding the mode and number of coordination around a metal ion on complex formation. The thermodynamic aspects of lanthanide complexation with various multidentate ligands provides a significant insight into understand the coordination chemistry of lanthanides in framing the relevant metal organic networks for the applications in biological, biochemical and medical aspects. The pyrazine carboxylic acids are known to form many structurally important complexes and further can form chelates with coordination number of eight for europium in which more water molecules can be knocked out from the primary coordination sphere than demanded by denticity of the ligand. The present studies aimed at ESI-MS characterization and determination of the thermodynamic parameters (log ß, ΔG, ΔH, and ΔS), luminescence properties of europium complexes with pyrazine-2-carboxylate and pyrazine-2,3-dicarboxylate in aqueous solutions by experiment as well as theory. Time resolved luminescence spectroscopy supported by DFT calculations are carried out to optimize the stable geometries of the complexes with various modes of binding and coordination. Furthermore, the thermodynamic parameters estimated theoretically have been used to trace the path of complex formation.

Breakdown of continuum model for water transport and desalination through ultrathin graphene nanopores: insights from molecular dynamics simulations.

In the quest for identifying a graphene membrane for efficient water desalination, molecular dynamics simulations were performed for the pressure-driven flow of salty water across a multilayer graphene membrane. Water transport through the graphene membranes was tuned as a function of pore size, external pressure, and salt concentration. The results predicted that water permeability through the graphene channel (width of h = 7 Å) is two orders of magnitude higher than that through the conventional thin film membranes. The breaking of continuum assumption in graphene nanopores was captured by the appearance of a layered water structure and plug-like velocity profiles. Furthermore, the fluidity under nano confinement of graphene was examined in terms of shear viscosity, friction coefficient, and slip length, which were found to depend on the separation of the confining graphene walls and the external pressure. Furthermore, the MD results revealed that the macroscopic water flux through the graphene nanopores can be linked to the microscopic diffusion of water. The calculated viscosity and diffusion coefficient under the graphene pores did not follow the Stokes-Einstein relation, indicating the failure of the hydrodynamic theory. The confined state of water in the graphene pores was also explored via the translational density of states (TDOS) and entropy, which displayed a significant change in the translational entropy with change in the pore size and applied pressure and thus revealed the interconnectivity of the structure, dynamics, thermodynamics, and hydrodynamics of water in the graphene nanopores. Such a linking of the microscopic parameters with the macroscopic profiles provides direct evidence to the experiments of pressure-driven flow through the graphene membranes and might be helpful in examining the performance of graphene membranes for the factors that have large implications on their application in the reverse osmosis (RO) process and other biological channels.

Molecular dynamics simulation for the test of calibrated OPLS-AA force field for binary liquid mixture of tri-iso-amyl phosphate and n-dodecane.

Tri-isoamyl phosphate (TiAP) has been proposed to be an alternative for tri-butyl phosphate (TBP) in the Plutonium Uranium Extraction (PUREX) process. Recently, we have successfully calibrated and tested all-atom optimized potentials for liquid simulations using Mulliken partial charges for pure TiAP, TBP, and dodecane by performing molecular dynamics (MD) simulation. It is of immense importance to extend this potential for the various molecular properties of TiAP and TiAP/n-dodecane binary mixtures using MD simulation. Earlier, efforts were devoted to find out a suitable force field which can explain both structural and dynamical properties by empirical parameterization. Therefore, the present MD study reports the structural, dynamical, and thermodynamical properties with different mole fractions of TiAP-dodecane mixtures at the entire range of mole fraction of 0-1 employing our calibrated Mulliken embedded optimized potentials for liquid simulation (OPLS) force field. The calculated electric dipole moment of TiAP was seen to be almost unaffected by the TiAP concentration in the dodecane diluent. The calculated liquid densities of the TiAP-dodecane mixture are in good agreement with the experimental data. The mixture densities at different temperatures are also studied which was found to be reduced with temperature as expected. The plot of diffusivities for TiAP and dodecane against mole fraction in the binary mixture intersects at a composition in the range of 25%-30% of TiAP in dodecane, which is very much closer to the TBP/n-dodecane composition used in the PUREX process. The excess volume of mixing was found to be positive for the entire range of mole fraction and the excess enthalpy of mixing was shown to be endothermic for the TBP/n-dodecane mixture as well as TiAP/n-dodecane mixture as reported experimentally. The spatial pair correlation functions are evaluated between TiAP-TiAP and TiAP-dodecane molecules. Further, shear viscosity has been computed by performing the non-equilibrium molecular dynamics employing the periodic perturbation method. The calculated shear viscosity of the binary mixture is found to be in excellent agreement with the experimental values. The use of the newly calibrated OPLS force field embedding Mulliken charges is shown to be equally reliable in predicting the structural and dynamical properties for the mixture without incorporating any arbitrary scaling in the force field or Lennard-Jones parameters. Further, the present MD simulation results demonstrate that the Stokes-Einstein relation breaks down at the molecular level. The present methodology might be adopted to evaluate the liquid state properties of an aqueous-organic biphasic system, which is of great significance in the interfacial science and technology.

Passage of TBP-uranyl complexes from aqueous-organic interface to the organic phase: insights from molecular dynamics simulation.

The present study reports molecular dynamics simulations for biphasic systems comprising tributyl phosphate (TBP) in dodecane and uranyl nitrate in the aqueous phase, which are key chemical species in the well-known Pu-U extraction (PUREX) process. An attempt has been made to understand the nature of interface and mechanism of 'TBP associated uranyl' crossing under neutral and acidic conditions. Results show that the solvent density undergoes large fluctuation near the interface depending on the nature of the aqueous-organic phase. The study provides compelling evidence of experimentally observed reorganization of interfacial complexes at the interface and their structural reformation during extraction. It has been observed that the surface active nature of TBP and their interfacial coverage is modulated by the nature of incorporated solute species and their location with respect to the interface. Also, the TBP structuring near the interface is destroyed when an acidic interface is considered rather than a neutral one which favors the uranyl extraction. With an acidic interface, the water humidity of organic phase was observed to be increased in the experiments. Furthermore, the acid/water solubility in the organic phase was observed to be influenced by selection of acid models and their concentration. Simulations with high acid concentration show water pocket formation in the organic phase. However, in the case of dissociated ions or a mixture of both, no such water pool is observed and the extracted water remains dispersed in the organic phase, having the tendency to be replaced by HNO3 because of preferred TBP·HNO3 complexation over TBP·H2O. Most remarkably, the present study makes evident the TBP-induced charge redistribution of uranyl complexes during migration from the interface to the bulk organic phase, which contributes to drive uranyl complexes such as UO2·NO3·4TBP, UO2·5TBP and UO2·NO3·3TBP·HNO3 in the organic phase, and this was reestablished by DFT calculations. Thus, the present study inspires future simulation and experimental investigations on the extraction of species at the liquid-liquid interface.

Uniqueness of Nanoscale Confinement for Fast Water Transport: Effect of Nanotube Diameter and Hydrophobicity.

Inspired by the enhanced water permeability of carbon nanotubes (CNTs), molecular dynamics simulations were performed to investigate the transport behavior through nanotubes made of boron nitride (BNNT), silicon carbide (SiC), and silicon nitride (SiN) alongside carbon nanotubes (which have different hydrophobic attributes) considering their implication for reverse osmosis (RO) membranes under different practical environments. According to our findings, not only do CNTs but also other kinds of nanotubes exhibit transition anomalies with increasing diameter. Utilizing the robust two-phase thermodynamic (2PT) methods, the current examinations shed light on thermodynamic origin of favorable water filling of these nanotubes. The results show that regardless of the nanotube material, the filling of water inside small nanopores (d < 10 Å) as well as within pores of diameter larger than 15 Å will always be favored by the entropy of filling. However, the entropic preference for filling nanotubes with a diameter of 10-15 Å depends on the constituent material. In particular, the enhancement in total entropy of confined water was mainly due to the increased rotational freedom of confined water molecules. The thermodynamic origin of water transport was correlated with the structural and fluidic behavior of water inside these nanotubes. The observed data for density, flow, structure correlation functions, water-water coordination, tetrahedral order parameter, hydrogen bonds, and density of states functions quantitatively support the observed entropy behavior. Of critical importance is that the present study demonstrates the effectiveness of RO filtration using nanotubes of boron nitride rather than carbon. Furthermore, it was found that one should avoid the use of silicon nanotubes unless filtration needs to be performed under harsh environments where nanotube of other materials cannot survive. Specifically, the results show that both the structural and dynamic properties of water confined in BNNTs are similar to those of CNT's, and for SiNT it is similar as SiC. Our results show that besides the nanotube material, the chirality index of the nanotube also plays a significant role in determining the structure, dynamics and thermodynamics of confined water molecules.

Quantum chemical pathways for the formation of 2,3,7,8-tetrachloro dibenzo-p-dioxin (TCDD) from 2,4,5-trichlorophenol: a mechanistic and thermo-kinetic study.

CONTEXT: Dioxins, specifically 2,3,7,8-tetrachlorinated dibenzo-p-dioxin (TCDD), are highly toxic dioxins known for their severe health impacts and persistent environmental pollutants. This study focuses on understanding the formation pathways of TCDD from its precursor molecule 2,4,5-trichlorophenol (2,4,5-TCP). In our exploration of reaction pathways from 2,4,5-trichlorophenol (TCP), we delve into three reaction mechanisms: free-radical, direct condensation, and anionic. Our findings highlight the significance of the radical mechanism, particularly propagated by H radicals, with a notable increase in dioxin formation around 900 K. These results are consistent with experimental observations indicating an increase in the conversion of trichlorophenol from 600 to 900 K in the non-catalytic gas phase reaction. Thermodynamic parameters (∆H, ∆S, and ∆G), reaction barriers, and rate constants (k) were calculated across a temperature range of 300-1200 K to support the findings and provide insights into the optimal temperature range for controlling dioxins during the incineration process. METHOD: In this study, quantum chemical calculations were conducted using density functional theory (DFT) with the B3LYP functional and the 6-311 + + G(d,p) basis set in Gaussian 16 software. Stationary points, including transition states (TS), were confirmed with frequency calculations. Intrinsic reaction coordinate (IRC) calculations ensured minimum energy paths between TS and products, visualized in GaussView 6.0 Program. Single-point energy calculations utilized a more precise basis set, 6-311 + + G(3df,2p), for enhanced energy accuracy, incorporating zero-point vibrational energy (ZPE) and other energy corrections. These calculations were repeated over a temperature range of 298.15-1200 K at 1 atm pressure. Finally, rate constant (k) expressions associated with TCDD formation were determined using transition state theory (TST).

Unusual redox stability of pentavalent uranium with hetero-bifunctional phosphonocarboxylate: insight into aqueous speciation.

The +5 state is an unusual oxidation state of uranium due to its instability in the aqueous phase. As a result, gaining information about its aqueous speciation is extremely difficult. The present work is an attempt in that direction and it provides insight into the existence of a new pentavalent species in the presence of hetero-bifunctional phosphonocarboxylate (PC) chelators, other than the carbonate ion, in the aqueous medium. The aqueous chemistry of pentavalent uranium species with three environmentally relevant PCs was probed using electrochemical and DFT methods to understand the redox energy and kinetics of conversion of the U(VI)/U(V) couple, stability, structure, stoichiometry, binding modes, etc. Interestingly, pentavalent uranium complexes with PCs are quite persistent over a wide range of pH starting from acidic to alkaline conditions. The PC chelators block the cation-cation interaction (CCI) of U(V) through strong hetero-bidentate chelation and intermolecular hydrogen bonding (IMHB) interactions which stabilize the pentavalent metal ion against disproportionation. For uranyl species in the presence of PCs, acting as chelators, CV plots were obtained at varying pH values from 2 to 8. The obtained results indicate an irreversible single redox peak involving U(VI) to U(V) conversion and association of a coupled chemical reaction with the electron transfer step. ESI-MS studies were performed to understand the speciation effect on the U(VI)/U(V) redox couple with varying pH. Speciation modelling of U(V) with the PC ligands was carried out, which indicated that the U(V) is redox stable in nearly 47% of the pH region in the presence of the PCs as compared to the carboxylate-based chelators. The free energy and reduction potential of the U(V) complexes and the reduction free energy and disproportionation free energy for the U(VI)/U(V) couple were determined by DFT computations in the presence of the PCs. In situ spectroelectrochemical spectra were recorded to provide evidence for the existence of U(V) species with PCs in the aqueous medium and to acquire its absorption spectra. The present study is highly significant for understanding the coordination chemistry of pentavalent uranium species, accurate modelling of uranium, and isolation of U(V).

Application of hybrid MOF composite in extraction of f-block elements: Experimental and computational investigation.

An attempt was made to understand the sorption behaviour of UO22+, Th4+ and Eu3+ on novel hybrid metal-organic framework composites, FeBDC@CoBDC. The XRD pattern revealed the composite nature of the hybrid MOF materials, while FTIR and Raman spectroscopic analyses evidenced the presence of different functional moieties. The thermal stability of the hybrid MOF composites was investigated through thermogravimetric analysis. The sorption predominantly followed Langmuir isotherm with sorption capacity of 189 mg g-1, 224 mg g-1 and 205 mg g-1 for UO22+, Th4+ and Eu3+ respectively. The sorption proceeded through chemisorption following pseudo 2nd order rate kinetics. The processes were found to be thermodynamically favourable and endothermic in nature. However, they were entropically driven. Multiple contacts of complexing agents were necessary for quantitative elution of f-elements from loaded MOF. The MOF showed moderate stability towards radiation exposure. DFT calculation was used for the optimization of structures, estimation of bond length and estimation of binding energy. In hybrid MOF composites, the Fe atom was having six coordination with 4 O atoms of BDC moieties and 2 O atoms of -OH groups. The O atoms of BDC and -OH groups were coordinated to Eu, Th and U atoms during their sorption.

The aqueous interaction of neodymium with two omni existent biomoieties - a mechanistic understanding by experimental and theoretical studies.

Neodymium (Nd), a technologically important metal ion, has emerged as a major contaminant in aquatic systems in recent years owing to its surge in electrical and electronic applications as a permanent magnet. The chelating molecules present in hydro- and biospheres could substantially enhance its absorption and lead to transportation and migration of Nd from the source. The mechanistic understanding of the Nd interaction with naturally relevant biomoieties present in flora and fauna is of primitive importance to estimate the toxicological effects of the metal ion. The present studies aimed at understanding the aquatic interaction of Nd with two biomoieties namely pyrazine-2-carboxylic acid (P2C) and pyrazine-2,3-dicarboxylic acid (P23C) by multiple experimental determinations and theoretical estimations. Potentiometry and spectrophotometry were employed to determine the aquatic speciation and thermodynamic stability of the complexes. Both techniques supported the formation of MLi (i = 1-4) complexes by Nd(III) with P2C and MLi (i = 1-3) complexes with P23C. The Nd-P23C complexes are more stable than the Nd-P2C complexes for ML formation, while the opposite trend is observed for the ML2 and ML3 complexes. Titration calorimetry was used to determine the enthalpies of complexation which was found to be exothermic and majorly favored by entropy contributions. The formation of the Nd(III)-P2C complexes is more exothermic than that of the respective Nd(III)-P23C complexes. Density functional theory was employed for the geometry optimization of the predicted complexes and for the estimation of the bond distances and partial charges on the coordinating atoms in the optimized geometries. Experimental insights provide crucial inputs at the macro (thermodynamic) level and theoretical calculations help in understanding the complexation process at the molecular level.