A detailed Rayleigh scattering model has been implemented and used to post-process detonation wave numerical simulation results to allow for a direct comparison with previous experimental visualizations of detonations in hydrogen-based mixtures. A quantum chemistry approach has been employed to obtain realistic Rayleigh scattering cross-sections. A database of Rayleigh cross-sections for relevant species was created and validated against available experimental data. Steady one-dimensional as well as unsteady two-dimensional simulations of detonation were used for comparison with experimental Rayleigh profiles and images. We demonstrate that both realistic Rayleigh scattering cross-sections and the characteristics of the imaging system have to be taken into account to accurately reproduce the experimental results. We show how this approach can be applied to estimate the performance and design improved Rayleigh imaging systems. Rayleigh scattering appears to offer some advantages over other techniques for studying the structure of detonation waves both at and behind the front. (C) 2015 The Combustion Institute. Published by Elsevier Inc. All rights reserved.