Luciano T. Costa

A Quantum Chemistry Study for Ionic Liquids Applied to Gas Capture and Separation

In recent years, the global climate change is in evidence and it is almost a consensus that it is caused by the greenhouse gases emissions. An alternative to reduce these emissions is carbon capture and storage (CCS), which employs solvents based on amine compounds. In this scene, ionic liquids (IL) have been investigated to a greater extent for this application. In this work, we make an evaluation of interactions between gases (CO2, SO2, and H2S) and anion/cation from IL, as well as cation-anion interactions. For this, quantum calculations under vacuum were performed at the B3LYP/6-311+G** level of theory and using the M06-2X functional, where dispersion effects are considered. Among the well-studied systems based on imidazolium cations and fluorinated anions, we also studied the tetraalkylammonium, tetraalkylphosphonium, ether-functionalized imidazolium based systems, and tetrahexylammonium bis(trifluoromethanesulfonyl)imide, [THA][Tf2N], as a potential prototype. The ion pairs evaluated include [Tf2N](-)-based IL, with alkyl chain varying from [C1mim](+) to [C8mim](+) and [C1mim](+)-based IL. We found that the anion becomes more available to interact with gas with the weakening of the cation-anion interaction. [THA][Tf2N] has a binding energy of -274.89 kJ/mol at the B3LYP/6-311+G** level of theory, which is considered energetically interesting to gas capture applications.

Insights on the Solubility of CO2 in 1-Ethyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide from the Microscopic Point of View

Emissions of greenhouse gases due to human activities have been well documented as well as the effects on global warming resulting from it. Efforts to reduce greenhouse gases at the source are crucial to curb climate change, but due to insignificant economic incentives to reduce usage of fossil fuels, not a lot of progress has been made by this route. This necessitates additional measures to reduce the occurrence of greenhouse gases in the atmosphere. Here we used theoretical methods to study the solubility of carbon dioxide in ionic liquids (ILs) since sequestration of CO2 in ILs has been proposed as a possible technology for reducing the emissions of CO2 to the atmosphere. Ionic liquids form a class of solvents with melting temperatures below 100 °C and, due to very low vapor pressures, which are not volatile. We have performed molecular dynamics (MD) simulations of 1-ethyl-3-methylimidazolium (C2mim) bis(trifluoromethylsulfonyl)imide (Tf2N) and its mixtures with carbon dioxide in order to investigate the CO2 concentration effect on the CO2-cation and CO2-anion interactions. A systematic investigation of CO2 concentration effects on resulting equilibrium liquid structure, and the local environment of the ions is provided. The Quantum Theory of Atoms in Molecules (QTAIM) was used to determine the interaction energy for CO2-cation and CO2-anion complexes from uncorrelated structures derived from MD simulations. A spatial distribution function analysis demonstrates the specific interactions between CO2 and the ionic liquid. Our findings indicate that the total volume of the system increases with the CO2 concentration, with a molar volume of CO2 of about 0.038 L/mol, corresponding to liquid CO2 under a pressure of 100 bar. In other words, the IL effectively pressurizes the CO2 inside its matrix. The thermodynamics of CO2 solvation in C2 min-Tf2N were computed using free energy techniques, and the solubility of CO2 is found to be higher in this IL (-3.7 ± 1 kcal/mol) than in water (+0.2 kJ/mol), predominantly due to anion-CO2 interactions.

Ion transport in polycarbonate based solid polymer electrolytes: experimental and computational investigations

Among the alternative host materials for solid polymer electrolytes (SPEs), polycarbonates have recently shown promising functionality in all-solid-state lithium batteries from ambient to elevated temperatures. While the computational and experimental investigations of ion conduction in conventional polyethers have been extensive, the ion transport in polycarbonates has been much less studied. The present work investigates the ionic transport behavior in SPEs based on poly(trimethylene carbonate) (PTMC) and its co-polymer with ε-caprolactone (CL) via both experimental and computational approaches. FTIR spectra indicated a preferential local coordination between Li(+) and ester carbonyl oxygen atoms in the P(TMC20CL80) co-polymer SPE. Diffusion NMR revealed that the co-polymer SPE also displays higher ion mobilities than PTMC. For both systems, locally oriented polymer domains, a few hundred nanometers in size and with limited connections between them, were inferred from the NMR spin relaxation and diffusion data. Potentiostatic polarization experiments revealed notably higher cationic transference numbers in the polycarbonate based SPEs as compared to conventional polyether based SPEs. In addition, MD simulations provided atomic-scale insight into the structure-dynamics properties, including confirmation of a preferential Li(+)-carbonyl oxygen atom coordination, with a preference in coordination to the ester based monomers. A coupling of the Li-ion dynamics to the polymer chain dynamics was indicated by both simulations and experiments.

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li(+) coordination and transportation were studied in the ternary electrolyte system, i.e., PEO16LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

Understanding the Solubility of Acetaminophen in 1-n-Alkyl-3-methylimidazolium-Based Ionic Liquids Using Molecular Simulation

During the manufacturing of pharmaceutical compounds, solvent mixtures are commonly used, where the addition of a cosolvent allows for the tuning of the intermolecular interactions present in the system. Here we demonstrate how a similar effect can be accomplished using a room temperature ionic liquid. The pharmaceutical compound acetaminophen is studied in 21 common ionic liquids composed of a 1-n-alkyl-3-methylimidazolium cation with 1 of 7 anions. Using the acetate anion, we predict a large enhancement in solubility of acetaminophen relative to water. We show how this is caused by a synergistic effect of favorable interactions between the ionic liquid and the phenyl, hydroxyl and amide groups of acetaminophen, demonstrating how the ionic liquid cation and anion may be chosen to preferentially solvate different functional groups of complex pharmaceutical compounds. Additionally, while the use of charge scaling in ionic liquid force fields has previously been found to have a minute effect on ionic liquid structural properties, we find it appreciably affects the computed solvation free energy of acetaminophen, which in turn affects the predicted solubility.

Inclusion complexes between cisplatin and oxidized carbon nanostructures: A theoretical approach

The toxicity of inclusion compounds formed by carbon nanostructures depends on its functionalized surface, use of solvents, dosage and other properties. Molecular modeling has potentially contributed to the understanding of the chemical nature of the formation of these systems and allows advancement in studies of the mechanism of transport, release of drugs and their biological implications. This work reports a quantum chemical investigation of the inclusion complexes formation between oxidized carbon nanotube (CNTox)/nanocone (CNCox) structure and cisplatin molecule, using the density functional theory (DFT) with the B3LYP functional and 6-31G(d,p)/LanL2DZ standard basis sets. Our results indicate that the cDDP@CNTox (inclusion complex - cisplatin into oxidized carbon nanotube) and cDDP@CNCox (inclusion complex - cisplatin into oxidized carbon nanocone) systems form stable molecular complexes that can be used as drug delivery devices. Our theoretical simulation of molecular spectra (IR, Raman and 1H NMR) reveals substantial changes due to complex formation that can be easily experimentally observed.

A molecular dynamics study of lithium-containing aprotic heterocyclic ionic liquid electrolytes

Classical molecular dynamics simulations were performed on twelve different ionic liquids containing aprotic heterocyclic anions doped with Li+. These ionic liquids have been shown to be promising electrolytes for lithium ion batteries. Self-diffusivities, lithium transference numbers, densities, and free volumes were computed as a function of lithium concentration. The dynamics and free volume decreased with increasing lithium concentration, and the trends were rationalized by examining the changes to the liquid structure. Of those examined in the present work, it was found that (methyloxymethyl)triethylphosphonium triazolide ionic liquids have the overall best performance.

Elucidating the Properties of Graphene–Deep Eutectic Solvents Interface

The properties of five deep eutectic solvents prepared based on the selection of choline chloride ionic liquid as hydrogen bond acceptor, which are mixed with several hydrogen bond donors with selected molecular features, were studied theoretically at graphene interfaces via both density functional theory and classical molecular dynamics methods. Molecular structuring at the interfaces, angular orientation, densification, and dynamic properties were analyzed upon adsorption on the graphene surface and when the deep eutectic solvents were confined between two graphene sheets and analyzed in terms of the role of the type of hydrogen bond donor for each solvent. Likewise, the behavior of deep eutectic solvent nanodroplets on graphene was simulated leading to the calculation of contact angles and nanowetting with further studies considering the effect of an external electric field on nanodroplet properties.

Natural polyprenylated benzophenone: keto-enol tautomerism from density functional calculations and the AIM theory

The quantum theory of atoms in molecules (QTAIM) and density functional theory (DFT) calculations were employed to investigate the structure and tautomeric equilibrium of epiclusianone, a polyisoprenylated benzophenone with interesting biological activities. Two different exchange-correlation functionals were employed, namely ωB97x-D and M06-2x, including implicit solvent models (benzene and DMSO). Our results for the thermodynamic properties show that the isomer in which the H atom is bonded to the oxygen away from the benzene ring is the most stable tautomer form of the epiclusianone, thus confirming previous charge density analysis from X-ray diffraction data (Martins et al. J Braz Chem Soc 18(8):1515–1523, 22).