title: CO2 Absorption Using Fluorine Functionalized Ionic Liquids: Interplay of Hydrogen and σ-Hole Interactions.
abstract: Use of ionic liquids (ILs) for CO2 capture offers certain advantages over currently used methodologies and is of growing interest. With this perspective, ILs composed of S-ethyl-N,N,N',N'-tetramethylthiouronium ([ETT]) and 1-hexyl-3-methylimidazolium ([Hmim]) cations and tris(pentafluoroethyl)trifluorophosphate ([FEP]) anion have been investigated. The present work unravels the noncovalent interactions accompanying CO2 capture by these ILs. Electronic structure of ion pairs and their CO2 absorbed [ETT][FEP]·n(CO2) and [Hmim][FEP]·n(CO2) (n up to 30) complexes are derived. The anisotropy in molecular electrostatic potential dictates the binding of CO2 through the interplay of (i) halogen bonding (O···F) between electron deficient σ-holes on fluorines, (ii) electrostatic C···F interactions between electron deficient carbons of CO2 and the electron-rich fluorine atoms, and the (iii) hydrogen bonding (O···H) interactions from the cation. The manifestations of these interactions on binding energies, polarizabilities, and vibrational spectra of CO2 absorbed complexes are presented. Consequent "frequency shift" accompanying hydrogen and halogen bonding exhibit complementary characteristics in the infrared spectra of CO2 absorbed complexes. Correlation of binding energies to absorbed CO2 molecules further demonstrate that [Hmim] based ILs are more efficient for CO2 capture applications.
authors: Department of Chemistry, Savitribai Phule Pune University , Pune 411 007, India.
authors: Soniya S
authors: SS
authors: Rao
authors: Department of Chemistry, Savitribai Phule Pune University , Pune 411 007, India.
authors: Shridhar P
authors: SP
authors: Gejji