Universal variational functionals of electron densities, first-order density matrices, and natural spin-orbitals and solution of the v-representability problem

摘要: Abstract Universal variational functionals of densities, first-order density matrices, and natural spin-orbitals are explicitly displayed for calculations ground states interacting electrons in atoms, molecules, solids. In all cases, the search constrained minima. particular, following Percus [Formula: see text] is identified as universal functional Hohenberg Kohn sum kinetic electron—electron repulsion energies an N-representable trial electron ρ. Q[ρ] searches antisymmetric wavefunctions Ψρ which yield fixed. then delivers that expectation value a minimum. Similarly, shown to be energy matrix γ, where actual external potential may nonlocal well local. These functions do not require function calculation associated with state some potential. Thus, v-representability problem, especially severe has been solved. Universal Hartree—Fock other restricted wavefunction theories also presented. Finally, spin-orbital theory compared traditional orbital formulations theory.