Chlorophyll a (Chl-a) is at the heart of solar energy capture and conversion in plants. Because of this, Chl-a has been the subject of innumerable studies. Recently, we have been able to use quantum mechanical methods to calculate the vibrational properties of neutral and oxidized Chl-a in the gas phase [Wang, R.; Parameswaran, S.; Hastings, G. Vib. Spectrosc. 2007, 44, 357-368]. The calculated vibrational properties do not agree with experiment, however. One factor ignored in our calculations was how solvents could impact the vibrational properties. Here we calculate the vibrational properties of Chl-a and Chl-a(+) in several solvents that span a wide range of dielectric constant. The calculated and experimental (Chl-a(+)-Chl-a) infrared difference spectra now show a remarkable similarity. However, the composition of the calculated vibrational modes are very different from that suggested from experiment. We therefore use our calculated data to make new suggestions as to the origin of the bands in experimental (Chl-a+-Chl-a) FTIR difference spectra. We indicate why bands in experimental spectra may have been misassigned. We also point to other experimental data that support our new band assignments. Assignment of bands in (Chl-a+-Chl-a) FTIR difference spectra were first made nearly 20 years ago. These assignments have formed the basis for evaluating all "cation minus neutral" FTIR difference spectra obtained for all photosynthetic systems since then. All of these experimental FTIR difference spectra should be re-examined in light of our new assignments.