The infrared and near-infrared spectra of acetylacetone, acetylacetone-d8, and hexafluoroacetylacetone are characterized from experiment and computations at different levels. In the fundamental region, the intramolecular hydrogen bonded OH-stretching transition is clearly observed as a very broad band with substantial structure and located at significantly lower frequency compared to common OH-stretching frequencies. There is no clear evidence for OH-stretching overtone transitions in the near-infrared region, which is dominated by the CH-stretching overtones of the methine and methyl CH bonds. From molecular dynamics (MD) simulations, with a potential energy surface previously validated for tunneling splittings, the infrared spectra are determined and used in assigning the experimentally measured ones. It is found that the simulated spectrum in the region associated with the proton transfer mode is exquisitely sensitive to the height of the barrier for proton transfer. Comparison of the experimental and the MD simulated spectra establishes that the barrier height is around 2.5 kcal/mol, which favorably compares with 3.2 kcal/mol obtained from high-level electronic structure calculations.