Computational quantum chemistry for single Heisenberg spin couplings made simple: just one spin flip required.

We highlight a simple strategy for computing the magnetic coupling constants, J, for a complex containing two multiradical centers. On the assumption that the system follows Heisenberg Hamiltonian physics, J is obtained from a spin-flip electronic structure calculation where only a single electron is excited (and spin-flipped), from the single reference with maximum Ŝz, M, to the M - 1 manifold, regardless of the number of unpaired electrons, 2M, on the radical centers. In an active space picture involving 2M orbitals, only one β electron is required, together with only one α hole. While this observation is extremely simple, the reduction in the number of essential configurations from exponential in M to only linear provides dramatic computational benefits. This (M, M - 1) strategy for evaluating J is an unambiguous, spin-pure, wave function theory counterpart of the various projected broken symmetry density functional theory schemes, and likewise gives explicit energies for each possible spin-state that enable evaluation of properties. The approach is illustrated on five complexes with varying numbers of unpaired electrons, for which one spin-flip calculations are used to compute J. Some implications for further development of spin-flip methods are discussed.