First-principles determination of Heisenberg Hamiltonian parameters for the spin-1/2 kagome antiferromagnet ZnCu3(OH)6Cl2

Abstract

Herbertsmithite (ZnCu3(OH)6Cl2) is often discussed as the best realization of the highly frustrated antiferromagnetic kagome lattice known so far. We employ density functional theory calculations to determine eight exchange coupling constants of the underlying Heisenberg Hamiltonian. We find the nearest neighbour coupling J1 to exceed all other couplings by far. However, next-nearest neighbour kagome layer couplings of 0.019 J1 and interlayer couplings of up to -0.035 J1 slightly modify the perfect antiferromagnetic kagome Hamiltonian. Interestingly, the largest interlayer coupling is ferromagnetic even without Cu impurities in the Zn layer. In addition, we validate our DFT approach by applying it to kapellasite, a polymorph of herbertsmithite which is known experimentally to exhibit competing exchange interactions.