Understanding X-ray Photoelectron Spectra of Ionic Liquids: Experiments and Simulations of 1-Butyl-3-methylimidazolium Thiocyanate
Ekaterina Gousseva, Scott D. Midgley, Jake M. Seymour, Robert Seidel, Ricardo Grau‐Crespo, Kevin R. J. Lovelock
Abstract
Im][SCN] ionic liquid was studied using ab initio molecular dynamics, and results were compared against previously published and new experimental X-ray photoelectron spectroscopy (XPS) data. The long-held assumption that initial-state effects in XPS dominate the measured binding energies is proven correct, which validates the established premise that the ground state electronic structure of the ionic liquid can be inferred directly from XPS measurements. A regression model based upon site electrostatic potentials and intramolecular bond lengths is shown to account accurately for variations in core-level binding energies within the ionic liquid, demonstrating the important effect of long-range interactions on the core levels and throwing into question the validity of traditional single ion pair ionic liquid calculations for interpreting XPS data.