Heisenberg exchange enhancement by orbital relaxation in cuprate compounds

We calculate the Heisenberg exchange J in the quasi-2D antiferromagnetic cuprates La2CuO4, YBa2Cu3O6, Nd2CuO4 and Sr2CuO2Cl2. We apply all-electron (MC)SCF and non-orthogonal CI calculations to [Cu2O11](18-), [Cu2O9](14-), [Cu2O7](10-) and [Cu2O7Cl4](14-) clusters in a model charge embedding. The (MC)SCF tripler and singlet ground states are well characterized by Cu2+ (d(x2-y2)) and O2-. The antiferromagnetic exchange is strongly enhanced by admiring relaxed (MC)SCF triplet and singlet excited states, in which a single electron is transferred from the central O ion to Cu. We ascribe this effect to orbital relaxation in the charge transfer component of the wavefunction. Close agreement with experiment is obtained.