Spin Configuration in the 1/3 Magnetization Plateau of Azurite Determined by NMR

High magnetic field $^{63,65}$Cu NMR spectra were used to determine the local spin polarization in the 1/3 magnetization plateau of azurite, Cu$_3$(CO$_3$)$_2$(OH)$_2$, which is a model system for the distorted diamond antiferromagnetic spin-1/2 chain. The spin part of the hyperfine field of the Cu2 (dimer) sites is found to be field independent, negative and strongly anisotropic, corresponding to $\approx$10 % of fully polarized spin in a $d$-orbital. This is close to the expected configuration of the "quantum" plateau, where a singlet state is stabilized on the dimer. However, the observed non-zero spin polarization points to some triplet admixture, induced by strong asymmetry of the diamond bonds $J_1$ and $J_3$.