Effect of probe energy and competing pathways on time-resolved photoelectron spectroscopy signals: the ring-opening of 1,3-cyclohexadiene

Tudorovskya, Maria, Minns, Russell and Kirrander, Adam (2018) Effect of probe energy and competing pathways on time-resolved photoelectron spectroscopy signals: the ring-opening of 1,3-cyclohexadiene. Physical Chemistry Chemical Physics. (doi:10.1039/c8cp02397b).

Record type: Article

Abstract

The ring-opening dynamics of 1,3-cyclohexadiene (CHD) following UV excitation is studied using a model based on quantum molecular dynamics simulations with the ab-initio multiconfigurational Ehrenfest (AI-MCE) method coupled to the Dyson orbital approach for photoionisation cross sections. Time-dependent photoelectron spectra are calculated for probe photon energies in the range 2-15 eV. The calculations demonstrate the value of universal high-energy probes, capableof tracking the full photochemical dynamics of the molecule, as well as the benefit of more selective, lower-energy probes. The predicted signal, especially with the universal probes, becomes highly convoluted due to the contributions from multiple reaction paths, rendering interpretation
difficult unless complementary measurements and theoretical comparisons are available.

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