Exploring hyperfine coupling in molecular qubits.

Molecular qubits represent a promising avenue for advancing quantum sensing and computing technologies, yet significant challenges remain in optimising their performance. Hyperfine coupling has a critical influence on molecular qubit properties. While previous studies have exhaustively investigated this phenomenon, a comprehensive understanding of the underlying mechanisms across different systems remains elusive. A benchmark test was performed using DFT to assess which methodology worked best to accurately predict hyperfine coupling constants in molecular qubits predominantly composed of V and Cu. We systematically analysed the decomposition of hyperfine coupling and examined how variations in coordination sphere and molecular geometry impact dipolar, isotropic and spin-orbit contributions. By modelling diverse systems, we demonstrate how molecular design can fine-tune hyperfine coupling contributions, either minimising overall interaction or enhancing coupling along specific axes. This study provides useful insights into the structure-property relationships governing hyperfine coupling mechanisms and assesses the accuracy of different choices of density functional, basis sets and relativistic corrections in the prediction of hyperfine coupling constants.