The search for a spin crossover transition in small sized π-conjugated molecules: a Monte Carlo study

The spin crossover transition in π-conjugated polymers is a complex phenomenon involving a balance between Coulomb interaction and collective lattice distortions. We explore such a transition with a minimal electronic model comprising a Hubbard-U on-site repulsive potential and both electron-phonon and hyperfine interactions. The model is then solved numerically for small molecules at finite temperature by Monte Carlo methods in the search for the spin crossover. This is done at the mean field level in the Hubbard-U interaction at half filling. We demonstrate that for a certain region of the parameter space there is a spin crossover, where the system transits from a low-spin to a high-spin state as the temperature increases. In close analogy to standard spin crossover in divalent magnetic molecules such a transition is entropy driven, with both the spin and the vibrational contributions to the entropy being relevant. Such a transition is practically unaffected by the hyperfine interaction, which only plays a minor role in determining the electronic properties.