Jahn-Teller effect in CH3D+ and CD3H+: conformational isomerism, tunneling-rotation structure, and the location of conical intersections.

High-resolution pulsed-field-ionization zero-kinetic-energy photoelectron spectra of CH(3)D and CD(3)H have been recorded at rotational resolution from the adiabatic ionization energy up to 600 cm(-1) of internal energy of the respective cations. The spectra are characterized by the effects of a large-amplitude pseudorotational motion exchanging the equivalent nuclei in each molecule. With increasing internal energy, a transition from the tunneling regime with splittings of the order of 1-10 cm(-1) to the free pseudorotation regime is observed. A theoretical model that treats the simultaneous rotational and pseudorotational motions and incorporates the effects of the geometric phase has been developed. The model provides the appropriate rovibronic symmetries in the C(3v)(M) molecular symmetry group and reaches a near-quantitative agreement with the experimental data. The complete group-theoretical analysis of the rovibronic problem is also given. The analysis of the spectra has revealed the existence of two different isomers for both CH(3)D(+) and CD(3)H(+), which differ in the bond length between the carbon atom and the unique ligand atom. All isomers are subject to a fast pseudorotational motion between three equivalent minima with a period of 3-5 ps in CH(3)D(+) and 18-28 ps in CD(3)H(+). The analysis has also provided the ordering of the tunneling sublevels for each isomer, which enables the location of the twofold conical intersections on the potential energy surface that could not be determined from experiments on CH(4) (+).