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 n3px, n3py, and n3pz are used to validate the theoretical results, which in turn allow retrieving a comprehensive kinetic model describing the mutual interactions of these states for the first time.
Highlights
The response of a molecule to photoexcitation is governed by the coupling of its electronic states
The mechanistic understanding of the initial processes in light-induced molecular excited-state dynamics is both of fundamental interest and essential for the development of various technological applications, for example efficient lightharvesting systems[1] or molecular machines.[2]
The first steps of these dynamics, which proceed in the femto- to picosecond range, are often accompanied by nonadiabatic population transfer between the excited states and can be observed in real time with ultrafast time-resolved spectroscopy.[3]
Summary
Potential energy surfaces of all electronic states of acetone were represented with a linear vibronic coupling (LVC) model[39,44] including all 24 vibrational degrees of freedom and 49 electronic states. This large number of states is necessary in order to include the important ππ* state at the reference geometry (S48). Additional analysis was carried out by dividing the set of trajectories into different energy windows and fitting their populations independently. See the Supporting Information for additional computational details.
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