We present results from simulations of vibrational energy and phase relaxation and electronic curve crossing using a multilevel formulation of Redfield theory, which demonstrate the shortcomings of the optical Bloch approximation and the importance of coherence transfer processes in the relaxation dynamics of multilevel systems. Specifically we show that for a harmonic well, energy relaxation can occur with retention of vibrational phase, and that for sufficiently strong electronic coupling, the product of an electronic curve crossing process can be formed vibrationally coherent even when no coherence is present in the initially excited state.