Conical intersection and coherent vibrational dynamics in alkyl iodides captured by attosecond transient absorption spectroscopy.

The photodissociation dynamics of alkyl iodides along the C-I bond are captured by attosecond extreme-ultraviolet (XUV) transient absorption spectroscopy employing resonant ∼20 fs UV pump pulses. The methodology of previous experiments on CHI [Chang et al., J. Chem. Phys. 154, 234301 (2021)] is extended to the investigation of a C-I bond-breaking reaction in the dissociative A-band of CHI, i-CHI, and t-CHI. Probing iodine 4d core-to-valence transitions in the XUV enables one to map wave packet bifurcation at a conical intersection in the A-band as well as coherent vibrations in the ground state of the parent molecules. Analysis of spectroscopic bifurcation signatures yields conical intersection crossing times of 15 ± 4 fs for CHI, 14 ± 5 fs for CHI, and 24 ± 4 fs for i-CHI and t-CHI, respectively. Observations of coherent vibrations, resulting from a projection of A-band structural dynamics onto the ground state by resonant impulsive stimulated Raman scattering, indirectly reveal multimode C-I stretch and CCI bend vibrations in the A-bands of CHI, i-CHI, and t-CHI.