Structural, dynamical, and electronic properties of the ionic liquid 1-ethyl-3-methylimidazolium...

We provide a microscopic insight, both structural and electronic, into the multifold interactions occurring in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM][TFSI] currently targeted for applications in next-generation low-power electronics and optoelectronic devices. To date, practical applications have remained hampered by the lack of fundamental understanding of the interactions occurring both inside the IL and at the interface with the substrate. Our first principles dynamical simulations provide accurate insights into the nature of bonding and non-bonding interactions, dynamical conformational changes and induced dipole moments, along with their statistical distributions, of this ionic liquid, that have so far not been completely unraveled. The mobilities of the two ionic species are obtained by long-lasting dynamical simulations at finite temperature, allowing simultaneous monitoring and quantification of the isomerization occurring in the IL. Moreover, a thorough analysis of the electronic structure and partial charge distributions characterizing the two components, the cation and anion, allow rationalization of the nature of the electrostatic interactions, hydrogen bonding properties of the two ionic counterparts, and the infra-red and dielectric response of the system, especially in the low frequency range, for the full characterization of the IL.