Theoretical Study on the Solvation of C₆₀Fullerene by Ionic Liquids II: DFT Analysis of the Interaction Mechanism

Abstract

As a continuation of our previous work (J. Phys. Chem. B, 2014, 118, 11330) on the solvation of C60 by ionic liquids (ILs) using Molecular Dynamic simulations, this paper reports a systematic density functional theory (DFT) analysis on the interaction mechanism between C60 and 24 different ionic liquids (belonging to the imidazolium, piperazinium, and cholinium groups). Properties such as binding energies, charge distributions, intermolecular interactions, or electronic structure were analyzed as a function of the selected ILs. The stronger IL-C60 interactions would be related with π-π stacking between the C60 surface and anions such as salycilate ([SA]). Likewise, the electronic structure analysis pointed to a well-defined relationship between the energetics of IL-C60 systems and IL features. Therefore, ILs with deep HOMO energies as well as weak interaction between both ions would be a priori good candidates for C60 solvation. Although only short-range interactions are studied in the framework of DFT, this work provides useful information for the rational design of ILs that could exhibit suitable features as C60 solvents.

Theoretical Study of Amino Acid-Based Ionic Liquids Interacting with Carbon Nanosystems

“…Fullerenes (C60, C180, C240, and C540), graphene, and single-walled nanotubes were described according to the parametrizations reported in a previous work . The interaction of ionic liquids with fullerene was previously characterized for other types of ionic liquids, showing charge transfer due to the ionic liquid–fullerene interaction; therefore, polarization effects were inferred and force fields involving atomic charges considering the charge transfer were used for molecular dynamics simulations. ,, Nevertheless, these force field parametrizations involving polarization effects do not lead to remarkable structural changes. Therefore, because the analysis of structuring is the main objective of the present work, nonpolarizable force fields were used for all simulations.…”

“…Most of the available studies on fullerene + IL considered traditional ILs such as those based on imidazolium cations and fluorinated anions, and the number of studied ILs was very limited. Considering these limitations, our research group reported systematic studies in which the solvation of fullerenes by a large collection of ILs was analyzed using density functional theory (DFT) and molecular dynamics (MD) approaches showing how the IL–fullerene interaction may be fine-tuned through the selection of suitable ions. − Another remarkable application involving fullerenes and ILs is the possible encapsulation of these ions inside the fullerene cavity, leading to endohedral fullerenes with IL. Although the experimental development of IL-based endohedral fullerenes has not been reported, a recent theoretical study reported by our group confirmed their suitability …”

Solubility of C60 and PCBM in Organic Solvents

“…Besides, we follow the recent work by Huang et al 63 and by Cheung et al 64 who utilized the equilibrium bond lengths of fullerene carbon as taken from gas-phase electron diffraction data. 65 Electronic polarizations on the carbon ball as effected by the surrounding polar solvent molecules 44,45,66,67 were not considered.…”

Colloid Chemistry of Fullerene Solutions: Aggregation and Coagulation

“…Room temperature ionic liquids, RTIL, like fullerenes, have long ceased to be exotic compounds, but their combination has been relatively little studied to date. Theoretical studies on C 60 with were performed by Fileti, Chaban, and Maciel [162][163][164][165] and Garcia et al [166,167], whereas Pádua group performed both experimental [168][169][170] and theoretic studies [168].…”