Monitoring non-adiabatic dynamics in CS2 with time- and energy-resolved photoelectron spectra of wavepackets

We report results from a novel fully ab initio method for simulating the time-resolved photoelectron angular distributions around conical intersections in CS2. The technique employs wavepacket densities obtained with the multiple spawning method in conjunction with geometry-and energy-dependent photoionization matrix elements. The robust agreement of the calculated molecular-frame photoelectron angular distributions with measured values for CS2 demonstrates that this approach can successfully illuminate, and disentangle, the underlying coupled nuclear and electronic dynamics around conical intersections in polyatomic molecules. (C) 2017 Elsevier B.V. All rights reserved.