Feb. 2017 – New article in Chemical Physics Letters:

Monitoring Non-adiabatic Dynamics in CS₂ with Time- and Energy-Resolved Photoelectron Spectra of Wavepackets

Kwanghsi Wang^(a) , Vincent McKoy^(a), Paul Hockett^(b), Albert Stolow^{(b, c, d)},Michael S. Schuurman^{(b, d),}

^a A. A. Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, California 91125, USA

^b National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6, Canada

^c Department of Physics, University of Ottawa, ON K1N 6N5 Canada

^d Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON, K1N 6N5, Canada

Highlights

• Time-resolved photoelectron angular distributions around conical intersections are studied.

• Ab initio multiple spawning method is applied to obtain wavepacket densities.

• Geometry and energy dependent photoelectron matrix elements are employed.

• Molecular and laboratory photoelectron angular distributions are used to illustrate the non-adiabatic dynamics.

• Photoelectron spectra are compared with measured values.

Abstract

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.

DOI: 10.1016/j.cplett.2017.02.014