Effects of probe energy and competing pathways on time-resolved photoelectron spectroscopy: the ring-opening of 1, 3-cyclohexadiene. Issue 26 (7th June 2018)

• Record Type: Journal Article
• Authors: Tudorovskaya, Maria; Minns, Russell S.; Kirrander, Adam
• Is Part Of: Physical chemistry chemical physics. Volume 20:Issue 26(2018)
• Page Start: 17714
• Page End: 17726
• Publication Date: 2018-06-07
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c8cp02397b
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Photoelectron spectra for the ring-opening dynamics of 1, 3-cyclohexadiene are studied using a model based on quantum molecular dynamics and the Dyson orbital approach. 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, capable of tracking the dynamics in full, but also the utility of more selective lower-energy probes with a more restricted ionisation range. The predicted signal, especially with the universal probes, becomes highly convoluted due to the contributions from multiple reaction paths, rendering interpretation challenging unless complementary measurements and theoretical comparisons are available.