Lineshape Distortions in Internal Reflection Two-Dimensional Infrared Spectroscopy: Tuning across the Critical Angle

[Image: see text] Reflection mode two-dimensional infrared spectroscopy (R-2DIR) has recently emerged as a tool that expands the utility of ultrafast IR spectroscopy toward a broader class of materials. The impact of experimental configurations on the potential distortions of the transient reflectance (TR) spectra has not been fully explored, particularly in the vicinity of the critical angle θ(c) and through the crossover from total internal reflection to partial reflection. Here we study the impact on the spectral lineshape of a dilute bulk solution as θ(c) is varied across the incident angle by tuning the refractive index of the solvent. We demonstrate the significance of several distortions, including the appearance of phase twisted lineshapes and apparent changes in the spectral inhomogeneity, and show how these distortions impact the interpretation of the TR and R-2DIR spectroscopies.