Abstract
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(IV) and Cu(II). 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.