Explorative computational study of the singlet fission process

Different ab initio methods, namely multi-reference and nonorthogonal configuration interaction techniques, are explored for their applicability in studying the singlet fission problem. It has been shown for 2-methyl-1,5-hexadiene that the ¹TT state can be identified using multi-reference techniques. The geometrical and vibrational properties of the ¹TT state are such that they can be approximated with those of the ⁵TT state. A proof of principle is given for the calculation of the singlet fission pathway driven by nuclear motion: efficient singlet fission can take place if the ¹TT and S₁ states are close in energy with a large non-adiabatic coupling matrix element at the S₁ geometry, and the energy of the S₀ state is well below that of the ¹TT state at the ¹TT geometry.

The nonorthogonal configuration interaction method was used to treat a tetracene trimer. It has been shown that the first excited states can be interpreted as delocalised states; interaction with charge-transfer base states plays an important role. The ¹TT states are localised on one pair of molecules. The electronic coupling between the diabatic Sn] and ¹TTm] states is in the meV range, confirming previous estimates. The charge-transfer base states enhance the coupling between the S1]/S2] and ¹TT2] excited states.