Medium and high resolution vacuum UV photoabsorption spectroscopy of methyl iodide (CH3I) and its deuterated isotopomers CD3I and CH2DI. A Rydberg series analysis

The vacuum UV photoabsorption spectrum of CH3I has been investigated between 5 eV and 20 eV. Numerous vibronic transitions are observed. In the high 10-20 eV photon energy range weak to very weak diffuse bands are observed and ascribed to electronic transitions from 3a(1), 1e and 2a(1) to Rydberg orbitals. In the 6-10.5 eV photon energy range more than 200 sharp and strong to weak lines have been observed. Several photon energy ranges were explored under high resolution conditions allowing us to observe many series up to high values of the principal quantum number n. They are assigned to vibration-less Rydberg transitions and classified into two groups converging to the two components of the spin-orbit split (X) over bar E-2 state of CH3I+. These two groups consist of six different Rydberg series, i.e., nsa(1), npa(1), npe, nda(1), nde and nf. A very close correlation has been established between the term values of the Rydberg states in CH3I and in Xe for ns, np, nd and nf Rydberg transitions. For the first time, the same measurements have been performed and the interpretation has been proposed for the photoabsorption spectrum of CH2DI and CD3I in the 6-10.5 eV photon energy range. For these two species, ionization energies are deduced: for the (X) over bar E-2(3/2) and (X) over bar E-2(1/2) states of CH2DI, these are IEad = 9.544 eV and IEad = 10.168 eV, respectively, and the corresponding energies are 9.552 eV and 10.173 eV in CD3I. (C) 2009 Elsevier B. V. All rights reserved.