Uniform spin chain physics arising from NCN bridges in CuNCN: surprises on the way from copper oxides to their nitride analogs

TL;DR

This study reveals unexpected uniform spin chain behavior in CuNCN, a copper nitride, with magnetic interactions mediated by NCN groups, differing from copper oxide analogs, and suggests potential for exotic properties and heat transport applications.

Contribution

The paper provides the first detailed microscopic model of CuNCN's magnetic interactions, highlighting the unique perpendicular exchange pathways and their implications.

Findings

Magnetic interactions are mediated perpendicular to structural chains via NCN groups.

The spin model aligns with temperature-independent susceptibility below 300 K.

CuNCN may exhibit ballistic heat transport and a pressure-induced metal-insulator transition.

Abstract

We report on the unexpected uniform spin chain physics in CuNCN, the insulating nitride analog of copper oxides. Based on full-potential band structure calculations, we derive the relevant microscopic parameters, estimate individual exchange couplings, and establish a realistic spin model of this compound. The structure of CuNCN contains chains of edge-sharing CuN(4) squares. As a surprise, in contrast to analogous [CuO(2)] chains in "edge-sharing" cuprates, the leading magnetic interactions J ~ 2500 K run perpendicular to the structural [CuN(2)] chains via bridging NCN groups. The resulting spin model of a uniform chain is in agreement with the experimentally observed temperature-independent magnetic susceptibility below 300 K. The nearest-neighbor and next-nearest-neighbor interactions along the structural [CuN(2)] chains are J(1) ~ -500 K and J(2) ~ 100 K, respectively. Despite the frustrating nature of J(1) and J(2), we assign the anomaly at 70 K to long-range magnetic ordering, which is likely collinear with antiparallel and parallel arrangement of spins along the 'c' and 'a' directions, respectively. The pronounced one-dimensionality of the spin system should lead to a reduction in the ordered moment and to a suppression of the transition anomaly in the specific heat, thus impeding the experimental observation of the long-range ordering. Our results suggest CuNCN as a promising material for ballistic heat transport within spin chains, while the sizable bandwidth W ~ 3 eV may lead to a metal-insulator transition and other exotic properties under high pressure.