Revealing Ultrafast Population Transfer between Nearly Degenerate Electronic States.

ABSTRACT: The response of a molecule to photoexcitation is governed by the coupling of its electronic states. However, if the energetic spacing between the electronically excited states at the Franck-Condon window becomes sufficiently small, it is infeasible to selectively excite and monitor individual states with conventional time-resolved spectroscopy, preventing insight into the energy transfer and relaxation dynamics of the molecule. Here, we demonstrate how the combination of time-resolved spectroscopy and extensive surface hopping dynamics simulations with a global fit approach on individually excited ensembles overcomes this limitation and resolves the dynamics in the n3p Rydberg states in acetone. Photoelectron transients of the three closely spaced states n3p_x, n3p

SUBMITTER: Heim P 

PROVIDER: S-EPMC7052817 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature