Report
Few-femtosecond electronic and structural rearrangements of CH$_4^+$ driven by the Jahn-Teller effect
| العنوان: | Few-femtosecond electronic and structural rearrangements of CH$_4^+$ driven by the Jahn-Teller effect |
|---|---|
| المؤلفون: | Zinchenko, Kristina S., Ardana-Lamas, Fernando, Lanfaloni, Valentina Utrio, Monahan, Nicholas, Seidu, Issaka, Schuurman, Michael S., Neville, Simon P., Woerner, Hans Jakob |
| سنة النشر: | 2023 |
| المجموعة: | Physics (Other) |
| مصطلحات موضوعية: | Physics - Chemical Physics, Physics - Optics |
| الوصف: | 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 $T_{\rm d}$ geometry to a nominal $C_{\rm 2v}$ 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 $D_{\rm 2d}$ structure. The methods demonstrated in our work provide guidelines for the understanding of Jahn-Teller driven non-adiabatic dynamics in other, more complex systems. Comment: 28 pages, 10 figures |
| نوع الوثيقة: | Working Paper |
| URL الوصول: | http://arxiv.org/abs/2311.14013 |
| رقم الانضمام: | edsarx.2311.14013 |
| قاعدة البيانات: | arXiv |
| الوصف غير متاح. |