The quantum chemical density matrix renormalization group (DMRG) algorithm is difficult to analyze because of the many numerical transformation steps involved. In particular, a decomposition of the intermediate and the converged DMRG states in terms of Slater determinants has not been accomplished yet. This, however, would allow one to better understand the convergence of the algorithm in terms of a configuration interaction expansion of the states. In this work, the authors fill this gap and provide a determinantal analysis of DMRG states upon convergence to the final states. The authors show that upon convergence, DMRG provides the same complete-active-space expansion for a given set of active orbitals as obtained from a corresponding configuration interaction calculation. Additional insight into DMRG convergence is provided, which cannot be obtained from the inspection of the total electronic energy alone. Indeed, we will show that the total energy can be misleading as a decrease of this observable during DMRG microiteration steps may not necessarily be taken as an indication for the pickup of essential configurations in the configuration interaction expansion. One result of this work is that a fine balance can be shown to exist between the chosen orbital ordering, the guess for the environment operators, and the choice of the number of renormalized states. This balance can be well understood in terms of the decomposition of total and system states in terms of Slater determinants.