Rydberg series in the near-uv vapour-phase absorption spectra of (η6-arene)2Cr(0) and (η6-arene)2 V(0) complexes

Electronic states of neutral and cationic bis(benzene) titanium and vanadium sandwich complexes studied by pulsed field ionization electron spectroscopy

“…In addition to these PES and PIE studies, the IE of V -bz 2 was measured as 6.16 ͑2͒ eV from Rydberg series in the near-ultraviolet absorption spectrum of the vanadium complex. 9 The large error reported in that study is somewhat surprising because Rydberg spectroscopy should in principle yield accurate ionization limits. However, the absorption spectrum of V -bz 2 was rather broad and the value of the quantum defect was not well defined in the original paper.…”

“…2,3 Table III compares the IE values of Ti-and V -bz 2 obtained from ZEKE spectroscopy with those from previous PES, 6,8 PIE,4,5,7 and Rydberg absorption spectroscopic measurements. 9 It can be seen from the table that accuracy of the Ti-and V -bz 2 IE values is greatly improved by this work due to very high ZEKE spectral resolution. The previous PES measurements reported a very large uncertainty ͑0.5 eV͒ for the IE of Ti-bz 2 .…”

“…6 The IEs of V -bz 2 were measured to be 5.75͑3͒ eV by PIE spectroscopy, 5,7 5.95 eV by He I and He II PES, 6,8 and 6.16͑2͒ eV by Rydberg series UV absorption spectroscopy. 9 Thus, our motivation was to investigate the ground electronic states and improve the IE values of these two complexes. In this work, Ti-bz 2 and V -bz 2 are prepared with the laser-ablation molecular beam technique and seeded in helium supersonic expansions.…”

In situ formation and electron-spectroscopic study of bis(arene) V and Cr compounds on a graphite surface

“…The absorption spectrum 43 of CrBz 2 vapor in the 2.7-5.3 eV range shows relatively narrow Rydberg transitions at 3.3 and 4.4 eV and a broad feature at $4.0 eV, which is assigned to a valence excitation. p* transition at $7.0 eV and two molecular excitations at $2.6 and 3.8 eV, both of which have been assigned 43 to transitions originating from the e 2g (HOMO-1) orbital. A recent calculation 44 using time-dependent DFT places the CrBz 2 a 1g !…”

Rydberg transitions in titanium sandwich complexes: Gas-phase and solution-phase photoabsorption study of (η7-C7H7)(η5-C5H5)Ti, (η8-C8H8)(η5-C5H5)Ti, and (η8-C8H8)(η5-C5Me5)Ti

“…Transition metal sandwich compounds appear to reveal in the gas-phase absorption spectra interesting features which arise from electronic transitions originating at the non-bonding metal a 1 (d z 2) level and terminating at Rydberg MOs. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] Molecular Rydberg orbitals are derived from the AOs with principal quantum numbers higher than those for valence-shell MOs. 20,21 They are atomic-like and can be characterised by azimuthal quantum numbers l. The l value determines the type of a Rydberg MO (s, p, d, ...).…”