Photochemical reactions on semiconductors are anisotropic, since they occur with different rates on surfaces of different orientations. Understanding the origin of this anisotropy is crucial to engineering more efficient photocatalysts. In this work, we use hybrid density functional theory to identify the surfaces associated with the largest number of photo-generated carriers in different semiconductors. For each material, we create a spherical heat map of the probability of optical transitions at different wave vectors. These maps allow us to identify the directions associated with the majority of the photo-generated carriers and can, thus, be used to make predictions about the most reactive surfaces for photochemical applications. The results indicate that it is generally possible to correlate the heat maps with the anisotropy of the bands observed in conventional band structure plots, as previously suggested. However, we also demonstrate that conventional band structure plots do not always provide all the information and that taking into account the contribution of all possible transitions weighted by their transition dipole moments is crucial to obtain a complete picture.