Quasi-one-dimensional uniform spin-$\frac{1}{2}$ Heisenberg antiferromagnet KNaCuP$_2$O$_7$ probed by $^{31}$P and $^{23}$Na NMR

TL;DR

This study characterizes KNaCuP$_2$O$_7$ as a nearly ideal one-dimensional spin-$1/2$ Heisenberg antiferromagnet through comprehensive experimental and theoretical investigations, revealing minimal inter-chain interactions and specific magnetic fluctuation behaviors.

Contribution

It provides detailed experimental and computational evidence confirming KNaCuP$_2$O$_7$ as a nearly perfect 1D Heisenberg antiferromagnet with negligible inter-chain couplings.

Findings

Magnetic susceptibility and NMR shift fit the 1D Heisenberg model with J/k_B ≈ 59 K.

Inter-chain couplings are negligibly small (<0.1 K), confirming one-dimensionality.

Magnetic long-range order occurs at very low temperatures (~0.38 K).

Abstract

We present the structural and magnetic properties of KNaCuP$_2$O$_7$ investigated via x-ray diffraction, magnetization, specific heat, and $^{31}$P NMR and $^{23}$Na NMR measurements and complementary electronic structure calculations. The temperature dependent magnetic susceptibility and $^{31}$P NMR shift could be modeled very well by the uniform spin-$1/2$ Heisenberg antiferromagnetic chain model with nearest-neighbour interaction $J/k_{\rm B}\simeq 58.7$ K. The corresponding mapping using first principles electronic structure calculations leads to $J^{\rm DFT}/k_{\rm B} \simeq 59$ K with negligibly small inter-chain couplings ($J^{\prime}/k_{\rm B}$, $J^{\prime \prime}/k_{\rm B} < 0.1$ K), further confirming that the system is indeed an one-dimensional uniform spin-$1/2$ Heisenberg antiferromagnet. The temperature-dependent unit cell volume could be described well using the Debye approximation with a Debye temperature of $\Theta_{\rm D} \simeq 294$ K, consistent with the heat capacity data. The diverging trend of the NMR spin-lattice relaxation rates ($^{31}1/T_1$ and $^{23}1/T_1$) imply the onset of a magnetic long-range-ordering at very low temperatures supporting the anticipated $T_{\rm N} \simeq 0.38$ K from the inter-chain couplings. Moreover, the NMR spin-lattice relaxation rates show the dominant contributions from uniform ($q=0$) and staggered ($q = \pm \pi/a$) spin fluctuations in the high and low temperature regimes, respectively mimicking one-dimensionality of the spin-lattice. We have also demonstrated that $^{31}1/T_1$ in high temperatures varies linearly with $1/\sqrt{H}$ reflecting the effect of spin diffusion on the dynamic susceptibility. Further, the inter-chain frustration also substantially impede the magnetic ordering rendering the spin-lattice a perfect one-dimensional uniform spin-$1/2$ Heisenberg antiferromagnet over a wide temperature range.