Density functional theory at finite temperatures (Q5903830)

A rigorous foundation of the density functional approach to quantum statistical mechanics is given. The starting point is the well-known quantum statistical variational principle stating that the grand- canonical density matrix minimizes the Gibbs free energy over the space of hermitian and positive definite density matrices with unit trace. The variational parameter is chosen to be the local density distribution defined as \[ \rho_{tr}(r)=Tr[{\hat \rho}_{tr}\sum^{N}_{i=1}\delta (r_ i-r)]. \] The variational procedure is performed as follows: One inroduces the local-space point transformation of the physical space \({\mathbb{R}}^ 3\), \(\vec r\to \vec r'=f(\vec r)\vec r/| \vec r|\); this transformation induces the unitary transformation in the Hilbert space of wave functions and, therefore, defines the conjugacy relation in the space of density matrices. This space becomes a disjoint union of equivalent classes. The minimization procedure is first performed within a given equivalent class and then over distinct classes. The relevant Euler-Lagrange equations are derived. As an illustration the rigorous formulation of temperature- dependent Hartree-Fock theory is obtained.