Femtosecond XUV–IR induced photodynamics in the methyl iodide cation

The time-resolved photodynamics of the methyl iodide cation (CH _3 I ^+ ) are investigated by means of femtosecond XUV–IR pump–probe spectroscopy. A time-delay-compensated XUV monochromator is employed to isolate a specific harmonic, the 9th harmonic of the fundamental 800 nm (13.95 eV, 88.89 nm), which is used as a pump pulse to prepare the cation in several electronic states. A time-delayed IR probe pulse is used to probe the dissociative dynamics on the first excited $\tilde {A}\enspace {}^{2}\mathrm{A}_{1}$ state potential energy surface. Photoelectrons and photofragment ions— ${\mathrm{C}\mathrm{H}}_{3}^{+}$ and I ^+ —are detected by velocity map imaging. The experimental results are complemented with high level ab initio calculations for the potential energy curves of the electronic states of CH _3 I ^+ as well as with full dimension on-the-fly trajectory calculations on the first electronically excited state $\tilde {A}\enspace {}^{2}\mathrm{A}_{1}$ , considering the presence of the IR pulse. The ${\mathrm{C}\mathrm{H}}_{3}^{+}$ and I ^+ pump–probe transients reflect the role of the IR pulse in controlling the photodynamics of CH _3 I ^+ in the $\tilde {A}\enspace {}^{2}\mathrm{A}_{1}$ state, mainly through the coupling to the ground state $\tilde {X}\enspace {}^{2}\mathrm{E}_{3/2,1/2}$ and to the excited $\tilde {B}\enspace {}^{2}\mathrm{E}$ state manifold. Oscillatory features are observed and attributed to a vibrational wave packet prepared in the $\tilde {A}\enspace {}^{2}\mathrm{A}_{1}$ state. The IR probe pulse induces a coupling between electronic states leading to a slow depletion of ${\mathrm{C}\mathrm{H}}_{3}^{+}$ fragments after the cation is transferred to the ground $\tilde {X}\enspace {}^{2}\mathrm{E}_{3/2,1/2}$ states and an enhancement of I ^+ fragments by absorption of IR photons yielding dissociative photoionization.