We describe a method to obtain absolute vibrational excitation probabilities of molecules scattering from a surface based on measurements of the rotational state, scattering angle, and temporal distributions of the scattered molecules and apply this method to the vibrational excitation of NO scattering from Au(111). We report the absolute excitation probabilities to the v = 1 and v = 2 vibrational states, rotational excitation distributions, and final scattering angle distributions for a wide range of incidence energies and surface temperatures. In addition to demonstrating the methodology for obtaining absolute scattering probabilities, these results provide an excellent benchmark for theoretical calculations of molecule-surface scattering.