Potential energy landscape (PEL) concepts have been useful in conceptualizing the effects of intermolecular interactions on dynamic and thermodynamic properties of liquids and glasses. "Basins", or regions of reduced potential energy associated with locally preferred molecular packing are important PEL features. The molecular configurations at the bottom of these basins are referred to as inherent structures (ISs). Experimental methods for directly characterizing PEL features such as these are rare, largely relegating PEL concepts to theory and simulation studies, and impeding their exploration in real systems. Recently, we showed that quasielastic neutron scattering (QENS) data from propylene carbonate (PC) exhibit signatures of picosecond timescale motion that are consistent with intrabasin motion and interbasin transitions [Cicerone et al., J. Chem. Phys., 2017, 146, 054502]. Here we present optically-heterodyne-detected optical Kerr effect (OHD-OKE) spectroscopy studies on PC. The data exhibit signatures of motion within and transitions between basins that agree quantitatively with and extend the QENS results. We show that the librational component of the OKE response corresponds to intrabasin dynamics, and the enigmatic intermediate OKE response corresponds to interbasin transition events. The OKE data extend the measurement range of these parameters and reveal their utility in characterizing PEL features of real systems.