The vinoxide study leads to several interesting conclusions. It demonstrates that IR cryo-SEVI can be applied to polyatomic anions. Excitation of the vinoxide CO stretch at 1570 cm -1 yields a photoelectron spectrum that is readily interpreted and assigned within the harmonic approximation that is typically used for the interpretation of photoelectron spectra. The significant differences between the results at 1570 and 2546 cm -1 shows that at the higher vibrational frequency, effects attributed to anharmonic coupling in both the vinoxide anion and vinoxy radical are quite prominent but nonetheless can be analyzed using vibrational perturbation theory. The ability to spectroscopically determine which modes are coupled through anharmonic interactions complements previous work on intramolecular vibrational energy redistribution in polyatomic neutral molecules, most notably the IR chemiluminescence studies of McDonald and co-workers. As further applications of IR cryo-SEVI are explored, the extent to which anharmonic coupling grows in with increasing vibrational excitation and complexity of the molecule will play a major role in understanding this new experimental method.