Photoionization and dissociative photoionization of acetaldehyde in the 10.0-13.7 eV range by synchrotron photoelectron photoion coincidence spectroscopy.

Photoionization and dissociative photoionization of acetaldehyde (CH3CHO) in the 10.0‒13.7 eV energy range are studied by using synchrotron radiation double imaging photoelectron photoion coincidence spectroscopy (i2PEPICO). The X2A' and A2A" electronic states of CH3CHO+ as well as the Franck-Condon gap region between these two states have been populated with several vibrational sequences and assigned in the high-resolution slow photoelectron spectrum (SPES). The adiabatic ionization energies (AIEs) of the X2A' and A2A" states are measured at 10.228 ± 0.006 and 12.52 ± 0.05 eV, respectively. The present results show that the X2A' state is a stable state while the A2A" state is fully dissociative to produce CH3CO+, CHO+ and CH4+ fragment ions. The 0K appearance energies (AE0K) of CH3CO+ and CHO+ fragment ions are determined through the modeling of the breakdown diagram, i.e., AE0K(CH3CO+) = 10.89 ± 0.01 eV (including a reverse barrier of ~ 0.19 eV) and AE0K(CHO+) = 11.54 ± 0.05 eV. In addition, the dissociation mechanisms of CH3CHO+ including statistical dissociation, direct bond breaking and isomerization are discussed with the support of the calculated dissociation limits and transition state energies.

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