Singlet and triplet instability theorems

Tomonori Yamada, So Hirata
2015 Journal of Chemical Physics  
A benchmark theoretical study of the electronic ground state and of the singlet-triplet split of benzene and linear acenes A useful definition of orbital degeneracy-form-degeneracy-is introduced, which is distinct from the usual energy-degeneracy: Two canonical spatial orbitals are form-degenerate when the energy expectation value in the restricted Hartree-Fock (RHF) wave function is unaltered upon a two-electron excitation from one of these orbitals to the other. Form-degenerate orbitals tend
more » ... rate orbitals tend to have isomorphic electron densities and occur in the highest-occupied and lowest-unoccupied molecular orbitals (HOMOs and LUMOs) of strongly correlated systems. Here, we present a mathematical proof of the existence of a triplet instability in a real or complex RHF wave function of a finite system in the space of real or complex unrestricted Hartree-Fock wave functions when HOMO and LUMO are energyor form-degenerate. We also show that a singlet instability always exists in a real RHF wave function of a finite system in the space of complex RHF wave functions, when HOMO and LUMO are formdegenerate, but have nonidentical electron densities, or are energy-degenerate. These theorems provide Hartree-Fock-theory-based explanations of Hund's rule, a singlet instability in Jahn-Teller systems, biradicaloid electronic structures, and a triplet instability during some covalent bond breaking. They also suggest (but not guarantee) the spontaneous formation of a spin density wave (SDW) in a metallic solid. The stability theory underlying these theorems extended to a continuous orbital-energy spectrum proves the existence of an oscillating (nonspiral) SDW instability in one-and three-dimensional homogeneous electron gases, but only at low densities or for strong interactions. C 2015 AIP Publishing LLC. [http://dx.
doi:10.1063/1.4929354 pmid:26395692 fatcat:evyl6sbhwzdctcuzi4rjvox66e