Future 2D IR experiments will reveal critical cross peaks that encode intra-and intermolecular couplings and interactions. Here, the absence of ESA signals will be beneficial for resolving cross peaks within congested spectral regions. 2D experiments will require a pump pulse pair to resolve the excitation axis via a two-dimensional Fourier transform over the pump and probe pair time delays. Alternative data collection schemes, such as sparse sampling, will be necessary to reduce the total time needed to obtain a spectrum. Alternatively, scanning a frequency-resolved picosecond pump pulse might provide a better approach for resolving the excitation axis if sub-ps time resolution is not required. For transient UV/Vis-IR spectroscopy, electronic excitation with a UV/Vis pulse to initiate a reactive process should result in larger changes in the IR spectra that evolve more discernably as a reaction proceeds on excited electronic potential energy surfaces. An additional benefit here is that fewer phase cycling steps are required with a non-IR pump pulse to isolate the transient signal. Overall, transient and 2D spectroscopies on isolated molecular ion systems will play an important new role in unraveling reaction mechanisms at the molecular-level, which are often too difficult to elucidate with current condensed-phase methodologies, particularly for electron and proton transfer reactions.