Improved evaluation of spin-polarization energy contributions using broken-symmetry calculations

International audienceSpin-polarization effects may play an important role in free radicals and in the magnetic coupling between radical centers. Starting from restricted open-shell calculations, i.e. a closed-shell description of the non-magnetic core electrons, a low-order perturbation expansion identifies the spin polarization contribution to the energy of mono-radicals and to singlet-triplet energy differences in diradicals. Broken-symmetry (BS) single-determinant calculations introduce only a fraction of spin polarization effects, and in a biased manner, since BS determinants are not spin eigenfunctions. We propose a simple technique to correctly evaluate spin-polarization energies by taking into account the effect of spin-flip components of one-hole one-particle excited configurations. Spin-decontamination corrections is shown to play a non-negligible role in BS evaluation of bond energies. The importance of spin-decontamination is illustrated on cases for which spin polarization is the leading contribution to the singlet-triplet gap, what characterizes twisted conjugated double-bonds and disjoint diradicals