Jahn-Teller effect in tetrahedral symmetry: large-amplitude tunneling motion and rovibronic structure of CH4+ and CD4+

The energy level structures of the ground vibronic states of 12CH4+, 13CH4+, and 12CD4+ have been measured by pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopy. The nuclear spin symmetries of the tunneling-rotational levels have been determined in double-resonance experiments via selected rotational levels of the v3=1 and v3=2 vibrational levels of the X 1A1 ground state of CH4. The energy level structures of 12CH4+, 13CH4+, and 12CD4+ have been analyzed with an effective tunneling-rotational Hamiltonian. The analysis together with a group theoretical treatment of the Tx(e+t2) Jahn-Teller effect in the Td(M) group prove that the equilibrium geometry of 12CH4+, 13CH4+, and 12CD4+ has C2v symmetry and characterize the pseudorotational dynamics in these fluxional cations. The tunneling behavior is discussed in terms of the relevant properties of the potential energy surface, some of which have been recalculated at the CCSD(T)/cc-pVTZ level of ab initio theory.