Photoionization Bands of Cyanogen: Multi‐Mode Vibronic Coupling and Renner‐Teller Effects

Multi-mode vibronic coupling in the X˜2Πg${{\tilde{X}}^{2}{\Pi }_{g}}$ , A˜2Σg+${{\tilde{A}}^{2}{\Sigma }_{g}^{+}}$ , B˜2Σu+${{\tilde{B}}^{2}{\Sigma }_{u}^{+}}$ and C˜2Πu${{\tilde{C}}^{2}{\Pi }_{u}}$ electronic states of Cyanogen radical cation (C 2${{}_{2}}$ N 2.+${{}_{2}^{.+}}$ ) is investigated with the aid of ab initio quantum chemistry and first principles quantum dynamics methods. The electronic degenerate states of Π symmetry of C 2${{}_{2}}$ N 2.+${{}_{2}^{.+}}$ undergo Renner-Teller (RT) splitting along degenerate vibrational modes of π symmetry. The RT split components form symmetry allowed conical intersections with those from nearby RT split states or with non-degenerate electronic states of Σ symmetry. A parameterized vibronic Hamiltonian is constructed using standard vibronic coupling theory in a diabatic electronic basis and symmetry rules. The parameters of the Hamiltonian are derived from ab initio calculated adiabatic electronic energies. The vibronic spectrum is calculated, assigned and compared with the available experimental data. The impact of various electronic coupling on the vibronic structure of the spectrum is discussed.