High-resolution angular distributions of D(2) scattered from NiAl(110) have been measured at incident energies between 20 and 150 meV. The measurements were performed along the [110] azimuth using a high sensitivity time-of-flight apparatus, which allows the recording of diffraction channels not previously studied, including out-of-plane rotationally inelastic diffraction peaks. The attenuation of both elastic and rotationally inelastic diffraction intensities with surface temperature was found to follow a Debye-Waller model. The time-of-flight data analysis allowed us to assign unequivocally the different transition probabilities to each final state. In this way, 0→2, 2→0, and 1→3 transition probabilities were observed, covering relative intensities over two orders of magnitude. In the energy range investigated, the 0→2 transition was found to be a factor of 2-3 larger than the 2→0 one, which lies a factor of 10 above the 1→3 transition probability.