Electronic structure of the molecule-based magnet CuPM(NO3)2(H2O)2

Abstract

We present density-functional calculations on the molecule-based $S=\frac{1}{2}$ antiferromagnetic chain compound Cu $\mathrm{PM}{(\mathrm{N}{\mathrm{O}}_{3})}_{2}{({\mathrm{H}}_{2}\mathrm{O})}_{2}$. The properties of the ferro- and antiferromagnetic state are investigated at the level of the local-density approximation and with the hybrid functional B3LYP. Spin-density maps illustrate the exchange path via the pyrimidine molecule which mediates the magnetism in the one-dimensional chain. The computed exchange coupling is antiferromagnetic and in reasonable agreement with the experiment. It is suggested that the antiferromagnetic coupling is due to the possibility of stronger delocalization of the charges on the nitrogen atoms, compared to the ferromagnetic case. In addition, computed isotropic and anisotropic hyperfine interaction parameters are compared with recent NMR experiments.