Few-femtosecond electronic and structural rearrangements of CH${}_4^{+}$ driven by the Jahn-Teller effect

Abstract

The Jahn-Teller effect (JTE) is central to the understanding of the physical and chemical properties of a broad variety of molecules and materials. Whereas the manifestations of the JTE on stationary properties of matter are relatively well studied, the study of JTE-induced dynamics is still in its infancy, largely owing to its ultrafast and non-adiabatic nature. For example, the time scales reported for the distortion of CH${}_4^{+}$ from the initial $T_{\mathrm{d}}$ geometry to a nominal $C_{2v}$ relaxed structure range from 1.85~fs over 10$\pm$2~fs to 20$\pm$7~fs. Here, by combining element-specific attosecond transient-absorption spectroscopy and quantum-dynamics simulations, we show that the initial electronic relaxation occurs within 5~fs and that the subsequent nuclear dynamics are dominated by the $Q_2$ scissoring and $Q_1$ symmetric stretching modes, which dephase in 41$\pm$10~fs and 13$\pm$3~fs, respectively. Significant structural relaxation is found to take place only along the e-symmetry $Q_2$ mode. These results demonstrate that CH${}_4^{+}$ created by ionization of CH${}_4$ is best thought of as a highly fluxional species that possesses a long-time-averaged vibrational distribution centered around a $D_{2d}$ structure. The methods demonstrated in our work provide guidelines for the understanding of Jahn-Teller driven non-adiabatic dynamics in other, more complex systems.

28 pages, 10 figures