In a prior manuscript by Xu et al. [Xu, J.; Shen, X.; Knutson, J. R. J. Phys. Chem. A 2003, 107, 8383], time-resolved fluorescence emission anisotropy measurements were performed on perylene and tetracene in hexadecane using an upconversion technique with approximately 100 fs resolution. The anisotropy transients contained previously unseen decay terms of approximately 300 fs. In perylene, their amplitude corresponded to the " r(o) defect" that has gathered interest over decades. We ascribed this term to a predominantly in-plane libration. In this manuscript, we present molecular dynamics simulations for the motions of perylene and tetracene using the CHARMm molecular dynamics program (version c29b2). Both rotational correlation functions contain subpicosecond decay terms that resemble experimental anisotropy decays. It was suggested that the r(o) defect might arise from excited-state distortions of perylene, so we conducted quantum mechanical calculations to show that such distortion does not significantly displace the oscillators. We compare the case of perylene, with a strongly allowed singlet emission transition, to that of the weakly allowed tetracene transition. In perylene, motion alone can explain subpicosecond anisotropy decay, while tetracene decay also contains vibrational coupling terms, as previously reported by Sarkar et al. [Sarkar, N.; Takeuchi, S.; Tahara, T. J. Phys. Chem. A 1999, 103, 4808].