Photoelectron spectra of the group IVA halides

Relativistically parametrized extended‐Hückel calculations. II. Orbital energies of group‐IV tetrahalides and tetramethyls

“…Otherwise our labels agree with those of Egdell and Orchard [9]. The REX relativistic splittings of the t 1 HOMO also agree well with the experimental values.…”

“…Photoelectron spectra for the entire series MX4 (M = Ti, Zr, Hf; X = CI, Br, I) were reported by Egdell and Orchard [9]. Their results and assignments are shown as the right-most ones in Figure 1, together with the present EHT and REX ones, obtained using the single-(default parameters [4,5] for the metal and the double-( exponents in the Appendix for the halogens.…”

“…Figure I . Calculated and experimental (PES) orbital energies [9] for group-IVa halides. For each molecule the EHT.…”

The influence of relativistic effects on electronic energy levels in metal tetraiodides MI4 (M=Ti, Zr, Hf, Th)

“…The effects of spin-orbit coupling on metal tetrahalides has been considered previously [12,24,28,29]. Inclusion of the spin orbit effects splits the 2 T levels as shown in the descent of symmetry table (Table 4).…”

“…Here we explore the influence of scalar relativistic effects and spin-orbit coupling on the molecular electronic energy levels in the simple tetraiodides TiI 4 , ZrI 4 , HfI 4 and ThI 4 . The calculated molecular ionization energies are compared with previously published photoelectron spectra of the three transition metal halides [12]. The paper also presents experimental He(I) and He(II) photoelectron spectra of ThI 4 .…”