Enhancement of superexchange due to synergetic breathing and hopping in corner-sharing cuprates

Cuprates exhibit exotic states because of the interplay between spin, charge and orbital degrees of freedom. Ab initio calculations now show that a mechanism called orbital expansion plays a key role in the magnetic properties of cuprates. Cuprates with corner-sharing CuO4 plaquettes have received much attention owing to the discoveries of high-temperature superconductivity and exotic states where spin and charge or spin and orbital degrees of freedom are separated. In these systems spins are strongly coupled antiferromagnetically via superexchange mechanisms, with high nearest-neighbour coupling varying among different compounds. The electronic properties of cuprates are also known to be highly sensitive to the presence, distance and displacement of apical oxygens perpendicular to the CuO2 planes. Here we present ab initio quantum chemistry calculations of the nearest-neighbour superexchange antiferromagnetic (AF) coupling J of two cuprates, Sr2CuO3 and La2CuO4. The former lacks apical oxygens, whilst the latter contain two apical oxygens per CuO2 unit completing a distorted octahedral environment around each Cu atom. Good agreement is obtained with experimental estimates for both systems. Analysis of the correlated wavefunctions together with extended superexchange models shows that there is an important synergetic effect of the Coulomb interaction and the O-Cu hopping, namely a correlated breathing-enhanced hopping mechanism. This is a new ingredient in superexchange models. Suppression of this mechanism leads to drastic reduction in the AF coupling, indicating that it is of primary importance in generating the strong interactions. We also find that J increases substantially as the distance between Cu and apical O is increased.

Automated summary

Cuprates exhibit exotic states due to the interplay between spin, charge, and orbital degrees of freedom. Ab initio calculations reveal that the orbital expansion mechanism plays a key role in the magnetic properties of cuprates. Additionally, the electronic properties of cuprates are highly sensitive to the presence and displacement of apical oxygens perpendicular to the CuO2 planes, influencing the nearest-neighbour superexchange antiferromagnetic coupling.