Unusual spin fluctuations and magnetic frustration in olivine and non-olivine LiCoPO$_4$ detected by $^{31}$P and $^7$Li nuclear magnetic resonance

Abstract

We report $^{31}$P and $^{7}$Li nuclear magnetic resonance (NMR) studies in new non-olivine LiZnPO$_4$-type LiCoPO$_4^\text{tetra}$ microcrystals, where the Co$^{2+}$ ions are tetrahedrally coordinated. Olivine LiCoPO$_4$, which was directly transformed from LiCoPO$_4^\text{tetra}$ by an annealing process, was also studied and compared. The uniform bulk magnetic susceptibility and the $^{31}$P Knight shift obey the Curie-Weiss law for both materials with a high spin Co$^{2+}$ ($3d^7$, $S=3/2$), but the Weiss temperature $\Theta$ and the effective magnetic moment $\mu_\text{eff}$ are considerably smaller in LiCoPO$_4^\text{tetra}$. The spin-lattice relaxation rate $T_1^{-1}$ reveals a quite different nature of the spin dynamics in the paramagnetic state of both materials. Our NMR results imply that strong geometrical spin frustration occurs in tetrahedrally coordinated LiCoPO$_4$, which may lead to the incommensurate magnetic ordering.