Strong-field laser–molecule interaction forms much of the basis for initiating and probing ultrafast quantum dynamics. Previous studies aimed at elucidating the origins of vibrational coherences induced by intense laser fields have been confined to diatomic molecules. Furthermore, in all cases examined to date, vibrational wave packet motion is found to be induced by R-selective depletion; wave packet motion launched by bond softening, though theoretically predicted, remains hitherto unobserved. Here we employ the exquisite sensitivity of femtosecond extreme ultraviolet absorption spectroscopy to sub-picometer structural changes to observe both bond softening-induced vibrational wave packets, launched by the interaction of intense laser pulses with iodomethane, as well as multimode vibrational motion of the parent ion produced by strong-field ionization. In addition, we show that signatures of coherent vibrational motion in the time-dependent extreme ultraviolet absorption spectra directly furnish vibronic coupling strengths involving core-level transitions, from which geometrical parameters of transient core-excited states are extracted.

Studies of ultrafast molecular dynamics induced by intense laser fields can reveal new approaches to manipulating chemical reactions in the strong-field regime. Here, we show that intense few-cycle laser pulses can induce the spin-orbit state-selective C-I dissociation of the iodomethane cation (CHI) in the X̃ electronic state. Irradiation of CHI by 6 fs laser pulses with peak intensities of 1.9 × 10 W/cm followed by femtosecond extreme ultraviolet probing of the iodine 4d core-level transitions reveals dissociation of the CHI X̃ E state with a time constant of 0.76 ± 0.16 ps. By contrast, the X̃ E spin-orbit ground state does not exhibit any appreciable dissociation on the picosecond time scale. The observed spin-orbit state-selective dissociation of the X̃ state is rationalized in terms of the laser-induced coupling to the à state. Our results suggest that the intense-laser control of photodissociation channels can be potentially extended to spin-orbit split states.

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