I will present time-resolved measurements of the relaxation dynamics, in a small molecular system, following ultraviolet (UV) photoexcitation. We probe these excitations through photoionization and velocity map imaging (VMI) spectroscopy. Vacuum and extreme ultraviolet (VUV/XUV) pump and probe pulses are created by exploiting strong-field high harmonic generation (HHG) from our state-of-the-art 30 mJ, 1 kHz laser system. Three dimensional photoelectron and photoion momentum images recorded with our VMI spectrometer reveal non-Born Oppenheimer dynamics in the vicinity of a conical intersection, and allow us track the state of the system as a function of time. I will also present a series of experiments developing techniques for studying molecular dynamics at fourth generation, free electron laser (FEL), light sources.