On the thermodynamical analogy in spin-polarized density functional theory

The thermodynamical analogy of density functional theory, which is an organic part of the spin-independent version of the theory, is reconsidered for its spin-polarized generalization in view of the recently uncovered nonuniqueness of the external magnetic field B® corresponding to a given pair of density n® and spin density n_s®. For ground states, the nonuniqueness of B® implies the nondifferentiability of the energy functional E[n,n_s] with respect to n_s®. It is shown, on the other hand, that this nonuniqueness allows the existence of the one-sided derivatives of E[n,n_s] with respect to n_s®. Although the N-electron ground state can always be obtained from the minimization of E[n,n_s] without any constraint on the spin number N_s, the Lagrange multiplier mu_s associated with the fixation of N_s does not vanish even for ground states. Rather, mu_s is identified as the left- or right-side derivative of the total energy with respect to N_s. This justifies the interpretation of mu_s as a (spin) chemical potential, which is the cornerstone of the thermodynamical analogy.