**Abstract**

At present, the density functional theory (DFT) approach became the most widely used method for study molecules and solids. In the atmosphere of such great popularity, it is particularly important to know the limits of the applicability of DFT methods. In this chapter, I will discuss the modern state of DFT studies basing on the last publications and will consider in detail two cases when the conventional DFT approaches, in which used only electron density and its modifications by gradients, cannot be applied. First, the case related to the total spin S of the state. As I rigorously proved for an arbitrary N-electron state by group theoretical methods, the electron density does not depend on the total spin S of the state. From this follows that the Kohn-Sham equations have the same form for states with different S. The critical survey of elaborated DFT procedures, in which the spin is taken into account, shows that they modified only exchange functionals, and the correlation functionals do not correspond to the spin of the state. The point is that the conception of spin in principle cannot be defined in the framework of the electron density formalism, and this is the main reason of the problems arising in the study by DFT approaches the magnetic properties of the transition metals. The possible way of resolving spin problems can be found in the two-particle reduced density matrix formulation of DFT. In the end, it will be considered the case of the degenerated states, in which, as follows from the adiabatic approximation, the electron density may not be defined, since electronic and nuclear motions cannot be separated, since, the vibronic interaction mixed them.

**Keywords:** DFT, problem of spin in DFT, methods taking into account spinmultiplet structure, problem of degenerate states in DFT, vibronic interaction
