Raman spectroscopy has identified differences in how the anion conformer populations of alkali metal bis{(trifluoromethyl)sulfonyl}imide molten salts (Li-Cs) and protic 1-H-3-methylimidazolium [Hmim][NTf2] ionic liquids evolve with temperature. In the alkali metal systems, the trans-anion population grows with temperature as anticipated, whereas protic imidazolium ionic liquids show an increase in the more constrained cis-conformer. The objective of this work is (i) to examine changes in the anion cis/trans populations with temperature in thetwo systems in order to compare with, and ideally validate, results obtained from Raman spectroscopy data,and (ii) to generate an atomistic (ionic) description of differences in liquid structure, and subsequently cation-anion interaction modes present, with different types of cation.