The Jahn–Teller and pseudo-Jahn–Teller effects in hexafluorobenzene radical cation: nonradiative decay and radiative emission

state is energetically well separated from the other excited states. However, the rest of the states are closer in energy and they form low-energy conical intersections (CIs) leading to JT and PJT interactions. A vibronic coupling model is developed in a diabatic electronic basis employing symmetry selection rules, dimensionless normal displacement coordinates of the vibrational modes and Taylor series expansion of the elements of electronic Hamiltonian. Both time-independent and time-dependent quantum mechanical methods are employed in the nuclear dynamics calculations. The multi-configuration time-dependent Hartree (MCTDH) method is used for this purpose. Theoretical results are compared and found to be in good agreement with the available experimental data. The impact of the fluorination on the structure and dynamics of excited states is discussed in relation with the parent benzene radical cation.