This work explores the relationship between optimal control theory and adiabatic passage techniques in quantum systems. The study is based on a geometric analysis of the Hamiltonian dynamics constructed from the Pontryagin Maximum Principle. In a three-level quantum system, we show that the Stimulated Raman Adiabatic Passage technique can be associated to a peculiar Hamiltonian singularity. One deduces that the adiabatic pulse is solution of the optimal control problem only for a specific cost functional. This analysis is extended to the case of a four-level quantum system.