Consistent and efficient strategies to extract molecular magnetic interactions from computational calculations are needed. Mapping approaches, originally developed by Noodleman, use broken symmetry solutions to reconstruct spin adapted ones by means of a spin projector. However, that operator cannot always be defined. Below are my contributions to alternative ways of extracting magnetic interactions.
J. Chem. Theory Comput. 2015, 11, 3, 1006–1019
In heterodinuclear compounds, the spin projector that connects broken symmetry and spin adapted solutions is ill-defined. Here, we propose a way of correctly identifying broken symmetry solutions to consistently extract magnetic interactions based on a simple total spin expectation value.
J. Chem. Theory Comput. 2015, 11, 8, 3650–3660 & J. Chem. Theory Comput. 2016, 12, 7, 3228–3235
In the most general case of 3-electrons 3-centre problem, one does not have enough information to extract magnetic interactions from wavefunction-based methods. Here, we use Effective Hamiltonian Theory to validate values extracted by means of broken symmetry solutions.
J. Chem. Theory Comput. 2014, 10, 1, 335–345
m-xylylene is the archetypal diradical system and its small size allows for its description with extended wavefunction-based methods. Here, we interrogate its deceivingly complex electronic structure with a range of methods aimed at defining an accurate computational strategy to extract the magnetic interaction.
