Deep core photoionization of iodine in CH₃I and CF₃I molecules: how deep down does the chemical shift reach?

Abstract

Hard X-ray electron spectroscopic study of iodine 1s and 2s photoionization of iodomethane (CH3I) and trifluoroiodomethane (CF3I) molecules is presented.

Hard x-ray photoelectron spectroscopy on heavy atoms and heavy-element containing molecules using synchrotron radiation up to 35 keV at SPring-8 undulator beamlines

“…about 4.9 eV, we can extract the iodine 1s core-hole lifetime broadening Γ to be 9.65±0.43 eV, which corresponds to a lifetime τ of 68±3 as deduced using the standard formula  t G = / . We have also carried out similar measurements on the CH 3 I and CF 3 I molecules with slightly different photon energy, and we have extracted similar values which will be described elsewhere in detail together with the sophisticated theoretical calculations [43]. We notice that the extracted iodine 1s core-hole lifetime is very close to that of the adjacent Xe atom [34].…”

“…Therefore, we tentatively assign these peaks as originating from the double L 2,3 -hole hypersatellite Auger transitions. More detailed sophisticated calculations will be given elsewhere in near future [61].…”

Deep-core photoionization of krypton atoms below and above the 1s ionization threshold

“…The availability of high-resolution hard x-ray radiation up to 51 keV at SPring-8 [1] in Japan has opened new avenues for the study of heavy atoms and molecules with hard x-ray photoelectron spectroscopy (HAXPES), which is a powerful technique for the investigation of deep-core orbitals of different materials in a gas phase [1] or condensed matter [2]. In heavy atoms, either isolated or embedded in a molecule, this new possibility to create a very deep-core hole via singlephoton excitation or ionization enables direct studies of a multitude of interesting phenomena, such as core-hole lifetime in the attosecond range [3,4], direct observation of the relative weight of KL emission processes versus Auger relaxation [3], and partial charge redistribution within a molecule [4].…”

Electron spectroscopy and dynamics of HBr around the Br 1s−1 threshold

“…Similar differences have been observed for atomic 1s À1 ionization spectra of Xe 55 and Kr 38 as well as in I 1s À1 ionization of CH 3 I and CF 3 I in ref. 56. These differences can be understood by different population pathways leading to the L-hole states by ionization below and above the 1s À1 threshold.…”