Charge transfer and polarisability in ionic liquids: a case study

Philippi, Frederik; Goloviznina, Kateryna; Gong, Zheng; Gehrke, Sascha; Kirchner, Barbara; Pádua, Agı́lio A. H.; Hunt, Patricia A.

doi:10.1039/d1cp04592j

Cited by 16 publications

(8 citation statements)

References 115 publications

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“…As concluded in Figure d, the atomic ratios of different elements in anions are also considerably affected by the water content, among which O/N exhibits the most pronounced deviation. That is, the oxygen atom, through the O–H···O hydrogen bond, dictates the dominant interaction between H 2 O and [Tf 2 N] − , which is in good agreement with the simulation results that O has the maximum electronegativity in the [Tf 2 N] − anion . The O–H···O hydrogen bond is thought to weaken the electroneutrality of the anion, thus reducing the cation–anion interaction and confirming the structural conjecture aforementioned.…”

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confidence: 88%

Water-Controlled Structural Transition and Charge Transfer of Interfacial Ionic Liquids

Sun

et al. 2022

J. Phys. Chem. Lett.

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Clarification of the water-induced structural transitions and electron transfer between ionic liquids (ILs) and a solid surface allows for establishing a unified view of the electrical properties of interfacial ILs via a hitherto unexplored pathway. Here, we propose a simple and effective method to quantitatively identify and extract the transferred electrons between ILs and a solid surface, while demonstrating the critical structural transition of interfacial ILs from ordered stripe structures to disordered aggregation structures. The formation of hydrated anions, rooted in the hydrogen bonds of O–H···O between the anion and water, lies at the tipping point where electron transfer ends and aggregation structure begins. In addition, it is discovered to what extent the hydrophilicity of substrates can affect electron transfer, and a regulation method based on the electric field is explored. These experimental findings may refresh our knowledge of interfacial ILs and provide an effective method for evaluating the intrinsic electrical features of the ILs–solid surface.

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confidence: 88%

Water-Controlled Structural Transition and Charge Transfer of Interfacial Ionic Liquids

Sun

et al. 2022

J. Phys. Chem. Lett.

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“…Polarisable MD simulations were run using the LAMMPS 49 soware package, version 7 Aug 2019, ttdamp branch (the temperature grouped Nosé-Hoover thermostat (tgNH) is available in the USER-DRUDE package since version 24 Dec 2020). 50,51 We used the CL&Pol/TG-NH force eld as described previously, [51][52][53][54] with the standard force eld parameters for the [C 4 C 1 im] + cation and the [NTf 2 ] À anion. [55][56][57] The procedure of force eld extension to [CHTf 2 ] À anion is described in ESI.…”

Section: Molecular Dynamics Simulationsmentioning

confidence: 99%

Flexibility is the key to tuning the transport properties of fluorinated imide-based ionic liquids

et al. 2022

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“…The large underestimation of diffusion coefficients has motivated a large number of works aimed to developing polarizable models, as a speed up of ion dynamics upon including polarization effects was observed in the initial studies. ,− The polarization models built upon the fluctuating charge model, the classical Drude oscillator model, induced point dipoles and higher-order induced moments. Bedrov et al provide an excellent introduction and discussion to polarizable force fields, and we will not discuss these further.…”

Section: Simulationsmentioning

confidence: 99%

Theory and Simulations of Ionic Liquids in Nanoconfinement

et al. 2023

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Room-temperature ionic liquids (RTILs) have exciting properties such as nonvolatility, large electrochemical windows, and remarkable variety, drawing much interest in energy storage, gating, electrocatalysis, tunable lubrication, and other applications. Confined RTILs appear in various situations, for instance, in pores of nanostructured electrodes of supercapacitors and batteries, as such electrodes increase the contact area with RTILs and enhance the total capacitance and stored energy, between crossed cylinders in surface force balance experiments, between a tip and a sample in atomic force microscopy, and between sliding surfaces in tribology experiments, where RTILs act as lubricants. The properties and functioning of RTILs in confinement, especially nanoconfinement, result in fascinating structural and dynamic phenomena, including layering, overscreening and crowding, nanoscale capillary freezing, quantized and electrotunable friction, and superionic state. This review offers a comprehensive analysis of the fundamental physical phenomena controlling the properties of such systems and the current state-of-the-art theoretical and simulation approaches developed for their description. We discuss these approaches sequentially by increasing atomistic complexity, paying particular attention to new physical phenomena emerging in nanoscale confinement. This review covers theoretical models, most of which are based on mapping the problems on pertinent statistical mechanics models with exact analytical solutions, allowing systematic analysis and new physical insights to develop more easily. We also describe a classical density functional theory, which offers a reliable and computationally inexpensive tool to account for some microscopic details and correlations that simplified models often fail to consider. Molecular simulations play a vital role in studying confined ionic liquids, enabling deep microscopic insights otherwise unavailable to researchers. We describe the basics of various simulation approaches and discuss their challenges and applicability to specific problems, focusing on RTIL structure in cylindrical and slit confinement and how it relates to friction and capacitive and dynamic properties of confined ions.

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Charge transfer and polarisability in ionic liquids: a case study

Abstract: The practical use of ionic liquids (ILs) is benefiting from a growing understanding of the underpinning structural and dynamic properties, facilitated through classical molecular dynamics (MD) simulations. The predictive and...

Cited by 16 publications

References 115 publications

Water-Controlled Structural Transition and Charge Transfer of Interfacial Ionic Liquids

Water-Controlled Structural Transition and Charge Transfer of Interfacial Ionic Liquids

Flexibility is the key to tuning the transport properties of fluorinated imide-based ionic liquids

Theory and Simulations of Ionic Liquids in Nanoconfinement

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