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A theoretical investigation of the electron and phonon dynamics during intersubband transitions in undoped multiple GaAs-AlxGa1−xAs quantum well structures is presented within a rate equation formulation where particle and energy flow equations are derived from Boltzmann’s equation using Fermi statistics. This work focuses upon the role played by quantized polar optical phonons known as slab modes and interface modes. Photoexcited carrier behavior is analyzed in relation with recent Raman measurements and shows time constants for electron relaxation in agreement with experimental data.