Electronic and structural properties of the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulonyl)imide are studied using density functional theory (DFT) methods in addition to infrared and UV-vis spectroscopy. The DFT methods were conducted for both gas phase and solution phase using the integral equation formalism polarizable continuum model, while optical absorption experiments were conducted using neat and dilute methanol solutions. Three energetically similar conformers were obtained for each of the gas phase and solution phase DFT calculations. These multiple configurations were considered when analyzing the molecular interactions between the ion pair and for a molecular-level interpretation of the experimental IR and UV-vis spectroscopy data. Excitation energies of low-lying singlet excited states of the conformers were calculated with time-dependent DFT and experimentally with UV-vis absorption spectra. Difference density plots and excited-state calculations in the gas phase are found to be in good agreement with the experimental findings, while the implicit solvation model calculations adversely impacted the accuracy of the predicted spectra.