Journal of Physical Chemistry A, Vol.117, No.14, 3025-3033, 2013
Two-Dimensional Penning Ionization Electron Spectroscopy of Open-Shell Metallocenes: Outer Valence Ionic States of Vanadocene and Nickelocene
In order to investigate outer valence ionic states of open-shell metallocenes, we have applied two-dimensional collision-energy/electron-energy-resolved Penning ionization electron spectroscopy (2D-PIES) upon collision with metastable He*(2(3)S) excited atoms as well as a high level ab initio molecular orbital calculation (the partial third-order quasiparticle theory of the electron propagator (P3)) to ionization from neutral ground states of vanadocene ((4)A(2g)) and nickelocene ((3)A(2g)). Assignments of observed Penning ionization electron/He 1 ultraviolet photoelectron spectra were consistent with the P3 calculation results for ionization of alpha and beta spin electrons except for electron correlation bands observed by PIES. Negative collision energy dependence of partial Penning ionization cross-sections (CEDPICS) indicate attractive interaction with He*(2(3)S) around the molecule. Results by model potential calculation utilizing Li(2(2)S) instead of He*(2(3)S) for interaction between He*(2(3)S) and open-shell metallocenes do not explain the strong negative CEDPICS of the bands observed in PIES.