A variational method for the calculation of spin-rovibronic energy levels of triatomic molecules with three interacting electronic states

A general method is presented for the evaluation of the spin-rovibronic energy levels of triatomic molecules with up to three interacting potential energy surfaces. The full theory is outlined in detail, both for singlet and for doublet electronic states and the method is then applied to the benchmark example of C2H. High quality multireference configuration interaction calculations have been carried out to generate the 3dimensional near-equilibrium adiabatic potential energy surfaces of the three lowest 12Aʹ(X2~+), 22Aʹ(A2€), 12A"(A2€) electronic states of C2H, and the pair of interacting states of A ʹ symmetry have then been diabatized. Results are presented for J up to 7/2 and compared with gas-phase high resolution experimental results for energies up to 5600 cm-1.