Ring Opening and Rigidity: A Comparison of Time Resolved Photoelectron Spectroscopy Measurements and Calculations for 1,3-Cyclohexadiene and cis,cis-1,3-Cyclooctadiene

Time resolved photoelectron spectroscopy (TRPES) measurements can be directly compared with the same observable calculated using trajectory surface hopping calculations. In particular, 1,3-cyclohexadiene (CHD) and cis,cis-1,3-cyclooctadiene (COD) were compared to examine how size and rigidity can influence the dynamics, with the goal of developing systematic interpretations of how structural features can manifest differences in the dynamics. Though experimental data qualitatively agreed with theory for both molecules, CHD was found to have closer quantitative agreement, suggesting that some improvement in the theory is necessary to describe the dynamics accurately in general.