Theoretical study of intermolecular interactions in protic ionic liquids: a single ion pair picture

Abstract

Protic ionic liquids are made via intermolecular transfer between cation and anion. This research employs theoretical calculation to gain understanding of the intermolecular interactions at single-ion-pair level and their consequences to the macroscopic properties of the ionic liquids. The protic ionic liquids used in this study are ethylammonium nitrate (EAN), propylammonium nitrate (PAN), and butylammonium nitrate (BAN). Molecular structures of ions and ion pair of each liquid are optimized using the density functional theory. The ion pair binding energies and infrared spectra of optimized structures are investigated. Infrared spectra of separated cation and anion are compared with cation-anion ion pair to specify the vibrational band shifts due to intermolecular interactions. The infrared-spectra show the hydrogen-bond stretching modes in the far-infrared region at the wavenumber between 108-252 cm−1 and the red shifts of four vibrational bands due to intermolecular interactions between the ions. Three vibrational band shifts are mainly due to Coulomb force, and the other shift is caused by combination of intermolecular interactions. Moreover, the energy calculations show that the binding energy decreases as the alkyl chain length increases.

Effects of cation size on thermoelectricity of PEDOT:PSS/ionic liquid hybrid films for wearable thermoelectric generator application

“…41,43,73 However, the most efficient ionic liquids pair in enhanced conductivity from the longer alkyl chain in the cation species (in the case of HMIM BF 4 ) due to the lower binding energy between XMIM and BF 4 (ref. 74 and 75) guarantees a more favorable ion exchange with PEDOT:PSS, which screens their interaction with the doped PEDOT domains. As a result, the conductivity of the PEDOT:PSS films treated with ionic liquids monotonically decreases in the order of HMIM BF 4 > BMIM BF 4 > EMIM BF 4 > MMIM BF 4 ; the binding energy increases as the alkyl chain length of the cation decreases.…”