Journal of the Chemical Society, Faraday Transactions
Journal of the Chemical Society, Faraday Transactions; was published from 1990 - 1998. In 1999 it merged with a number of European chemical society physical Chemistry journals to become Physical Chemistry Chemical Physics.
Paper
J. Chem. Soc., Faraday Trans., 1998, 94, 2689 - 2694, DOI: 10.1039/a803515f
Ionic and Rydberg states of CF3I studied by high resolution photoelectron (ZEKE-PFI) and resonance-enhanced multiphoton ionisation spectroscopy
N. A. Macleod, S. Wang, J. Hennessy, T. Ridley, K. P. Lawley and R. J. Donovan
Ionic and Rydberg states of CF3I have been studied using both zero kinetic energy pulsed-field ionisation (ZEKE-PFI) photoelectron and resonance-enhanced multiphoton ionisation (REMPI) spectroscopy. The ground state of the ion (
2E3/2) was characterised using coherent two-photon (one-colour) ZEKE-PFI spectroscopy and extended progressions in the symmetric vibrational modes, similar to those observed in the conventional He(I) photoelectron spectrum, were observed at high resolution. The [2E3/2]6p Rydberg states were studied using two- and three-photon REMPI spectroscopy with linearly and circularly polarised light. This resulted in the assignment of at least three states with distinct 
values (2, 1 and 0) with the =2 components being the most intense. The strongest members of the [2E3/2]6p;2 system were used as resonant intermediates in two-colour (2+1
) ZEKE-PFI experiments which allowed the unambiguous assignment of the majority of the vibrational structure of the intermediate states. The adiabatic ionisation energy of CF3I was determined as 83652±2 cm-1. The vibrational structure observed for one of the =2 components of the [2E3/2]6p cluster in CF3I differs considerably from that observed for the lower lying 6s states and the analogous 6p states of CH3I. In particular, 
3 (the carbon–iodine stretch) shows a vibrational frequency substantially reduced from that of the neutral and ionic ground states. It is concluded that at least one of the [2E3/2]6p states of CF3I is distorted, possibly through an interaction with an ion-pair state.
