A Study of the Reactive Intermediate IF and I Atoms with Photoelectron Spectroscopy

Angle-resolved photoelectron (PE) spectra were recorded for IF and I. These were prepared as primary and secondary products of the F + CH2I2 reaction. PE spectra were recorded with different IF-to-I ratios to evaluate the relative intensities of IF and I photoelectron bands where their bands were overlapped. Improved values were obtained for the vertical and adiabatic ionization energies of the IF(+)(X(2)Pi(3/2)) <-- IF(X(1)sigma(+)) and IF(+)((2)Pi(1/2)) <-- IF(X(1)sigma(+)) ionizations and for the spectroscopic constants omega(e) and omega(e)ex(e) for the two IF ionic states X(2)Pi(3/2) and (2)Pi(1/2). Equilibrium bond lengths r(e) of these IF ionic states were derived from the experimental relative intensities of the vibrational components and calculated Franck-Condon factors. Threshold photoelectron (TPE) spectra were also recorded under the same reaction conditions. On comparing the TPE and PE spectra, the contributions from atomic iodine were much more intense in the TPE spectra. No difference was seen between the vibrational envelopes of the two observed IF bands, and no extra structure was seen associated with the TPE bands of IF as has been observed in TPE spectra of other diatomic halogens. The extra features that were observed in the TPE spectra can be assigned to contributions from autoionization of known I Rydberg states.