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Computational Modeling of Ionic Liquids and Solutions for Modern Applications

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A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Physical Chemistry and Chemical Physics".

Deadline for manuscript submissions: closed (30 June 2020) | Viewed by 18213

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Special Issue Editor

Prof. Dr. Jesse McDaniel

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Guest Editor

Georgia Institute of Technology, Atlanta, GA, USA

Special Issue Information

Dear Colleagues,

Computational simulations have become an extremely useful tool and complementary partner to experimental techniques for the investigation of myriad systems. The papers in this Special Issue are focused on the development of methods and application of computational techniques for the investigation of room temperature ionic liquids and related solutions. Target applications may include traditional fields of ionic liquid research targeting, e.g., solvation, catalysis, and electrochemistry, or alternatively may encompass newer “frontier” areas of ionic liquid research, such as IL-inspired materials and nanostructures or biochemical/biological applications. Articles may describe new physical insights or propose novel extension of well-studied ionic liquids, or instead focus on the development of entirely new types/classes of ionic liquids, e.g., amino acid-based ILs. The purpose of this collection is to highlight the broad applicability of state-of-the-art computational modeling to address open questions in ionic liquid-based systems. In this regard, it is anticipated that articles will encompass a wide range of modern computational techniques, including molecular simulation, ab initio methods, machine learning, and multiscale modeling approaches.

Prof. Dr. Gerardo Andrés Cisneros
Prof. Dr. Jesse McDaniel
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. International Journal of Molecular Sciences is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. There is an Article Processing Charge (APC) for publication in this open access journal. For details about the APC please see here. Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

computational simulations
solutions
ionic liquids
electrolytes

Published Papers (4 papers)

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Research

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19 pages, 5089 KiB

Open AccessArticle

Enantiomerization of Axially Chiral Biphenyls: Polarizable MD Simulations in Water and Butylmethylether

by Veronika Zeindlhofer, Phillip Hudson, Ádám Márk Pálvölgyi, Matthias Welsch, Mazin Almarashi, H. Lee Woodcock, Bernard Brooks, Katharina Bica-Schröder and Christian Schröder

Int. J. Mol. Sci. 2020, 21(17), 6222; https://doi.org/10.3390/ijms21176222 - 28 Aug 2020

Cited by 5 | Viewed by 3665

Abstract

In this study, we investigate the influence of chiral and achiral cations on the enantiomerization of biphenylic anions in n-butylmethylether and water. In addition to the impact of the cations and solvent molecules on the free energy profile of rotation, we also explore if chirality transfer between a chiral cation and the biphenylic anion is possible, i.e., if pairing with a chiral cation can energetically favour one conformer of the anion via diastereomeric complex formation. The quantum-mechanical calculations are accompanied by polarizable MD simulations using umbrella sampling to study the impact of solvents of different polarity in more detail. We also discuss how accurate polarizable force fields for biphenylic anions can be constructed from quantum-mechanical reference data. Full article

(This article belongs to the Special Issue Computational Modeling of Ionic Liquids and Solutions for Modern Applications)

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14 pages, 1892 KiB

Open AccessArticle

Accurate Diels-Alder Energies and Endo Selectivity in Ionic Liquids Using the OPLS-VSIL Force Field

by Caroline Velez, Brian Doherty and Orlando Acevedo

Int. J. Mol. Sci. 2020, 21(4), 1190; https://doi.org/10.3390/ijms21041190 - 11 Feb 2020

Cited by 14 | Viewed by 3435

Abstract

Our recently developed optimized potentials for liquid simulations-virtual site ionic liquid (OPLS-VSIL) force field has been shown to provide accurate bulk phase properties and local ion-ion interactions for a wide variety of imidazolium-based ionic liquids. The force field features a virtual site that offloads negative charge to inside the plane of the ring with careful attention given to hydrogen bonding interactions. In this study, the Diels-Alder reaction between cyclopentadiene and methyl acrylate was computationally investigated in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF₆], as a basis for the validation of the OPLS-VSIL to properly reproduce a reaction medium environment. Mixed ab initio quantum mechanics and molecular mechanics (QM/MM) calculations coupled to free energy perturbation and Monte Carlo sampling (FEP/MC) that utilized M06-2X/6-31G(d) and OPLS-VSIL gave activation free energy barriers of 14.9 and 16.0 kcal/mol for the endo-cis and exo-cis Diels-Alder reaction pathways, respectively (exptl. ΔH^‡ of 14.6 kcal/mol). The endo selectivity trend was correctly predicted with a calculated 73% endo preference. The rate and selectivity enhancements present in the endo conformation were found to arise from preferential hydrogen bonding with the exposed C4 ring hydrogen on the BMIM cation. Weaker electronic stabilization of the exo transition state was predicted. For comparison, our earlier ±0.8 charge-scaled OPLS-2009IL force field also yielded a ΔG^‡ of 14.9 kcal/mol for the favorable endo reaction pathway but did not adequately capture the highly organized solvent interactions present between the cation and Diels-Alder transition state. Full article

(This article belongs to the Special Issue Computational Modeling of Ionic Liquids and Solutions for Modern Applications)

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24 pages, 2093 KiB

Open AccessArticle

Tuning Water Networks via Ionic Liquid/Water Mixtures

by Archana Verma, John P. Stoppelman and Jesse G. McDaniel

Int. J. Mol. Sci. 2020, 21(2), 403; https://doi.org/10.3390/ijms21020403 - 8 Jan 2020

Cited by 23 | Viewed by 5528

Abstract

Water in nanoconfinement is ubiquitous in biological systems and membrane materials, with altered properties that significantly influence the surrounding system. In this work, we show how ionic liquid (IL)/water mixtures can be tuned to create water environments that resemble nanoconfined systems. We utilize molecular dynamics simulations employing ab initio force fields to extensively characterize the water structure within five different IL/water mixtures: [BMIM

^{+}

][BF

_{4}^{-}

], [BMIM

^{+}

][PF

_{6}^{-}

], [BMIM

^{+}

][OTf

^{-}

], [BMIM

^{+}

][NO

_{3}^{-}

] and [BMIM

^{+}

][TFSI

^{-}

] ILs at varying water fraction. We characterize water clustering, hydrogen bonding, water orientation, pairwise correlation functions and percolation networks as a function of water content and IL type. The nature of the water nanostructure is significantly tuned by changing the hydrophobicity of the IL and sensitively depends on water content. In hydrophobic ILs such as [BMIM

^{+}

][PF

_{6}^{-}

], significant water clustering leads to dynamic formation of water pockets that can appear similar to those formed within reverse micelles. Furthermore, rotational relaxation times of water molecules in supersaturated hydrophobic IL/water mixtures indicate the close-connection with nanoconfined systems, as they are quantitatively similar to water relaxation in previously characterized lyotropic liquid crystals. We expect that this physical insight will lead to better design principles for incorporation of ILs into membrane materials to tune water nanostructure. Full article

(This article belongs to the Special Issue Computational Modeling of Ionic Liquids and Solutions for Modern Applications)

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Review

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28 pages, 6918 KiB

Open AccessReview

Current Status of AMOEBA–IL: A Multipolar/Polarizable Force Field for Ionic Liquids

by Erik Antonio Vázquez-Montelongo, José Enrique Vázquez-Cervantes and G. Andrés Cisneros

Int. J. Mol. Sci. 2020, 21(3), 697; https://doi.org/10.3390/ijms21030697 - 21 Jan 2020

Cited by 25 | Viewed by 5074

Abstract

Computational simulations of ionic liquid solutions have become a useful tool to investigate various physical, chemical and catalytic properties of systems involving these solvents. Classical molecular dynamics and hybrid quantum mechanical/molecular mechanical (QM/MM) calculations of IL systems have provided significant insights at the atomic level. Here, we present a review of the development and application of the multipolar and polarizable force field AMOEBA for ionic liquid systems, termed AMOEBA–IL. The parametrization approach for AMOEBA–IL relies on the reproduction of total quantum mechanical (QM) intermolecular interaction energies and QM energy decomposition analysis. This approach has been used to develop parameters for imidazolium– and pyrrolidinium–based ILs coupled with various inorganic anions. AMOEBA–IL has been used to investigate and predict the properties of a variety of systems including neat ILs and IL mixtures, water exchange reactions on lanthanide ions in IL mixtures, IL–based liquid–liquid extraction, and effects of ILs on an aniline protection reaction. Full article

(This article belongs to the Special Issue Computational Modeling of Ionic Liquids and Solutions for Modern Applications)

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