Ultrafast relaxation investigated by photoelectron circular dichroism: an isomeric comparison of camphor and fenchone
Valérie Blanchet, D. Descamps, S. Petit, Y. Mairesse, B. Pons, B. Fabre
Abstract
, 4514]. Our measurements revealed a similar lifetime for both isomers. However, the circular dichroism in the photoelectron angular distribution decays exponentially in ∼730 fs from a +9% forward amplitude during the first hundreds of femtoseconds to reach an asymptotic -2% backward amplitude. This time-scale is drastically shorter than in fenchone. Our analysis allows us to evaluate the impact of the anisotropy of excitation; the relaxation dynamics, following photoexcitation by the linearly polarized pump, is then compared to that induced by a circularly polarized pump pulse (CPL). With such a CPL pump, we then retrieve time constants of our chiral observables similar to the ones recorded in fenchone. Quantum and classical simulations are developed and used to decipher the dependence of the PECD on the anisotropy of excitation and the spatial distribution of the 3s-Rydberg electron wavefunction. Our experimental investigations, supported by our simulations, suggest that varying the pump ellipticity enables us to reveal the breakdown of the Franck-Condon approximation.