Monitoring non-adiabatic dynamics in CS_2 with time- and energy-resolved photoelectron spectra of wavepackets

Abstract

We report results from a novel fully ab initio method for simulating the time-resolved photoelectron angular distributions around conical intersections in CS_2. 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 CS_2 demonstrates that this approach can successfully illuminate, and disentangle, the underlying coupled nuclear and electronic dynamics around conical intersections in polyatomic molecules.

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