Pitfalls on evaluating pair exchange interactions for modelling molecule-based magnetism

Abstract

Molecule-based magnetism is a solid-state property that results from the microscopic interaction between magnetic centres or radicals. The observed magnetic response is due to unpaired electrons whose coupling leads to a particular magnetic topology. Therefore, to understand the magnetic response of a given molecule-based magnet and reproduce the available experimental magnetic properties by means of statistical mechanics, one has to be able to determine the value of the J(AB) magnetic exchange coupling between radicals. The calculation of J(AB) is thus a key point for modelling molecule-based magnetism. In this Perspectives article, we will build upon our experience in modelling molecular magnetism to point out some pitfalls on evaluating J(AB) couplings. Special attention must be paid to the cluster models used to evaluate J(AB), which should account for cooperative effects among J(AB) interactions and also consider the environment (counterions, hydrogen bonding) of the two radicals whose interaction has to be evaluated. It will be also necessary to assess whether a DFT-based or a wavefunction-based method is best to study a given radical. Finally, in addition to model and method, the J(AB) couplings have to be able to adapt to changes in the magnetic topology due to thermal fluctuations. Therefore, it is most important to appraise in which systems molecular dynamics simulations would be required. Given the large number of issues one must tackle when choosing the correct model and method to evaluate J(AB) interactions for modelling magnetic properties in molecule-based materials, the "human factor" is a must to cross-examine and challenge computations before trusting any result.